EP0000342A1 - Photopolymerisable binders - Google Patents
Photopolymerisable binders Download PDFInfo
- Publication number
- EP0000342A1 EP0000342A1 EP78100236A EP78100236A EP0000342A1 EP 0000342 A1 EP0000342 A1 EP 0000342A1 EP 78100236 A EP78100236 A EP 78100236A EP 78100236 A EP78100236 A EP 78100236A EP 0000342 A1 EP0000342 A1 EP 0000342A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- benzophenone
- photopolymerizable
- contain
- bis
- radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 28
- -1 diaminobenzophenone compound Chemical class 0.000 claims abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 15
- 239000000976 ink Substances 0.000 claims abstract description 11
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract 2
- 239000012965 benzophenone Substances 0.000 claims description 17
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 13
- 150000008366 benzophenones Chemical class 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 231100000563 toxic property Toxicity 0.000 abstract description 3
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 20
- 239000000203 mixture Substances 0.000 description 11
- SVIDPUWUNCALBH-UHFFFAOYSA-N bis[4-[2-hydroxyethyl(methyl)amino]phenyl]methanone Chemical compound C1=CC(N(CCO)C)=CC=C1C(=O)C1=CC=C(N(C)CCO)C=C1 SVIDPUWUNCALBH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 4
- 238000003848 UV Light-Curing Methods 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical class NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- VIIZJXNVVJKISZ-UHFFFAOYSA-N 2-(n-methylanilino)ethanol Chemical compound OCCN(C)C1=CC=CC=C1 VIIZJXNVVJKISZ-UHFFFAOYSA-N 0.000 description 1
- QUASZQPLPKGIJY-UHFFFAOYSA-N 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound OCCOCCOCCOCCOC(=O)C=C QUASZQPLPKGIJY-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- AXDAQXHCBFFBRR-UHFFFAOYSA-N C(CCCO)O.CC(C(O)O)(C)C.OCC(C)(CO)C Chemical compound C(CCCO)O.CC(C(O)O)(C)C.OCC(C)(CO)C AXDAQXHCBFFBRR-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004303 annulenes Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- ZOGPJLBETGQSJD-UHFFFAOYSA-N bis[4-[2-(2-hydroxyethoxy)ethyl-methylamino]phenyl]methanone Chemical compound C1=CC(N(CCOCCO)C)=CC=C1C(=O)C1=CC=C(N(C)CCOCCO)C=C1 ZOGPJLBETGQSJD-UHFFFAOYSA-N 0.000 description 1
- QSNYUCLCRIGTQR-UHFFFAOYSA-N bis[4-[2-hydroxyethyl(propyl)amino]phenyl]methanone Chemical compound C1=CC(N(CCO)CCC)=CC=C1C(=O)C1=CC=C(N(CCC)CCO)C=C1 QSNYUCLCRIGTQR-UHFFFAOYSA-N 0.000 description 1
- GPVNKZKPYPBSKT-UHFFFAOYSA-N bis[4-[2-hydroxypropyl(methyl)amino]phenyl]methanone Chemical compound C1=CC(N(C)CC(O)C)=CC=C1C(=O)C1=CC=C(N(C)CC(C)O)C=C1 GPVNKZKPYPBSKT-UHFFFAOYSA-N 0.000 description 1
- DIFPMHWJCYFZBU-UHFFFAOYSA-N bis[4-[3-hydroxypropyl(methyl)amino]phenyl]methanone Chemical compound C1=CC(N(CCCO)C)=CC=C1C(=O)C1=CC=C(N(C)CCCO)C=C1 DIFPMHWJCYFZBU-UHFFFAOYSA-N 0.000 description 1
- QLEOLVFFTJMFDI-UHFFFAOYSA-N bis[4-[ethyl(2-hydroxyethyl)amino]phenyl]methanone Chemical compound C1=CC(N(CCO)CC)=CC=C1C(=O)C1=CC=C(N(CC)CCO)C=C1 QLEOLVFFTJMFDI-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/109—Polyester
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/114—Initiator containing
- Y10S430/124—Carbonyl compound containing
Definitions
- the invention relates to photopolymerizable binders for printing inks, coatings and printing plates based on at least one photopolymerizable olefinically unsaturated compound and optionally a polymeric binder component which contain an advantageous diaminobenzophenone compound as a photosensitizer.
- Benzophenone derivatives containing amino groups are known. 4,4'-bis (N-dimethylamino) benzophenone (Michler's ketone) and its use in photoinitiator systems or as a photosensitizer for photopolymerizable systems have been described particularly frequently (cf. DT-OS 15 22 359). It is a disadvantage of Michler's ketone that its toxic properties are unsatisfactory for some applications, further that its limited solubility in many organic solvents and its limited compatibility with some polar photopolymerizable binders leave something to be desired, which, if higher concentrations of photosensitizers are required, can easily cause clouding occur in the corresponding mixtures, which interfere with photopolymerization.
- the object of the present invention was to find a substitute for Michler's ketone for photopolymerizable binders, which has improved toxic properties, an improved compatibility with photopolymerizable mixtures and allows a versatile use as a photosensitizer or component in photoinitiator systems for photopolymerizable compositions.
- Examples of such compounds are 4,4'-bis (N- ⁇ -hydroxyethyl-N-methylamino) benzophenone, 4,4'-bis (N- ⁇ -hydroxyethyl-N-ethylamino) benzophenone, 4,4'- Bis (N- ⁇ -hydroxyethyl-N-propylamino) benzophenone, 4,4'-bis (N- ⁇ -hydroxypropyl-N-methylamino) benzophenone, 4,4'-bis (N-hydroxypropyl-N -methylamino) benzophenone, 4,4'-bis (N-hydroxyethoxyethyl-N-methylamino) benzophenone of the formula (II) further 4,4'-bis (N, N-dihydroxyalkylamino) benzophenones such as 4,4'-bis (N, N-di- ⁇ -hydroxyethylamino) benzophenone, 4,4'-bis (N, N -di- ⁇ -hydroxypropy
- N-hydroxyalkyl-N-alkyl-anilines or N, N-dihydroxyalkylanilines for the reaction with formaldehyde or paraformaldehyde in the presence of acid, asymmetrical derivatives of di- produce aminobenzophenones, the intermediates always resulting in the correspondingly substituted diaminodiphenylmethanes, which are then oxidized with oxygen, for example in the presence of chloranil and iron complexes of dihydrodibenzotetraaza annulene, into the appropriately substituted diaminobenzophenones. can be converted.
- the compounds used as photosensitizers according to the invention can then be easily isolated and purified as mostly acicular crystalline solid substances with melting points above 100 ° C.
- the diaminobenzophenone compounds used according to the invention in photopolymerizable binders have, with activity comparable to Michler's ketone as photosensitizer, the advantages that they are less toxic than Michler's ketone, better solubility in many organic solvents and with many polar photopolymeric. Mixtures that can be improved. point.
- a further known photoactivator in the binder according to the invention such as benzoin, benzoin ether, anthraquinone, benzil, benzil monoalkyl ketals, fluorenone, fluorene, diacetyl and in particular benzophenone or a low absorbent in the range from 300 to 380 nm Benzophenone derivative, such as those with an extinction coefficient ⁇ 360 nm ⁇ 200, it being possible to use the molar ratios and amounts known for the combination with Michler's ketone.
- Suitable photopolymerizable olefinically unsaturated compounds are the known low molecular weight monomers and oligomers (in particular with a molecular weight below 2,000) which are suitable for photopolymerizable binders.
- medium for printing inks, coating agents and for printing plates? are known per se, the nature of the monomers, of course, depending on the intended use and on the polymer binder which may be used, with which they should be compatible.
- Monomers with two or more olefinically unsaturated photopolymerizable double bonds alone or mixtures thereof with monomers with only one olefinically unsaturated photopolymerizable double bond are preferred, the proportion of monomers with only one double bond generally only being about 5 to 50 and preferably 5 to 30 percent by weight of the total amount of monomers is.
- Suitable olefinically unsaturated compounds are di- and polyacrylates and methacrylates, as can be prepared by esterification of diols or polyols with acrylic acid or methacrylic acid, such as the di- and tri (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol with a molecular weight up to about 500, 1,2-propanediol, 1,3-propanediol, neopentyl glycol (2,2-dimethyl propanediol) 1,4-butanediol, 1,1,1-trimethylol propane, glycerol or pentaerythritol; furthermore the monoacrylates and monomethacrylates of such diols and polyols, e.g.
- Ethylene glycol or di-, tri- or tetraethylene glycol monoacrylate monomers with two or more olefinically unsaturated bonds containing urethane groups and / or amide groups, such as the low molecular weight compounds prepared from aliphatic diols of the type mentioned above, organic diisocyanates and hydroxyalkyl (meth) acrylates .
- acrylic acid, methacrylic acid and their derivatives such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide or (meth) acrylates of monoalcohols with 1 to 6 carbon atoms.
- Binders according to the invention which contain polar monomers and / or polar polymeric binders, such as urethane acrylates or epoxy acrylates, have been very successful.
- suitable binder components and the use of the systems according to the invention reference is made to DT-OS 1 522 359, 2 200 478, 2 358 948, 2 441 148, the diaminobenzophenone compounds used according to the invention being able to replace the Michler ketone described there.
- Suitable polymeric binder components are e.g. Polyamides, polyurethanes, unsaturated polyesters and polyester urethanes.
- the photopolymerizable binders according to the invention can be mixed in a known manner with the usual additives, such as thermal polymerization inhibitors, dyes, plasticizers, etc.
- the greater solubility of the photosensitizers used according to the invention when they are used for adequate curing of highly pigmented photopolymerizable systems, in particular when using highly absorbent pigments, for example in UV-curing printing inks with opaque black.
- the prints achieved here show a greatly improved brilliance.
- the binders of the invention are particularly suitable less than 10 / um for UV-curing printing inks, but also for offset printing plate coatings and as a photoresist material in layer thicknesses.
- a UV-curable binder is produced by homogeneously mixing the components at 90 to 100 ° C, consisting of 20% of a urethane acrylate (produced by reacting an aliphatic biuret isocyanate with stoichiometric amounts of hydroxypropyl acrylate), 64% of a further urethane acrylate (produced by reacting hexamethylene diisocyanate) with stoichiometric amounts of hydroxypropyl acrylate), 10% butanediol diglycidyl ether diacrylate, 3% benzophenone and 3% 4,4'-bis (N-ß-hydroxyethyl-N-methylamino) benzophenone.
- the UV-curable binder is clear even after 3 months of storage at room temperature.
- a UV-curable binder is produced exactly as stated in Example 2, but instead of 3% 4,4'-bis (N- ⁇ -hydroxyethyl-N-methylamino) benzophenone, 3% 4,4'-bis (N -dimethylamino) benzophenone used.
- the binder is stored exactly like that of Example 2 for about 3 months at room temperature, but then shows a clear cloudiness due to fine crystals.
- a homogeneous mixture of 52% of an epoxy resin acrylate (produced by reacting a bisphenol A epichlorohydrin resin with an epoxy equivalent weight of 190 with 97 mol%, based on the epoxy groups, pure acrylic acid), 40% pentaerythritol tetraacrylate, 4% bezophenone and 4% 4,4'-bis (N- ⁇ -hydroxyethyl-N-methylamino) benzophenone is stored for 3 months at room temperature. The mixture remains clear and unclouded.
- Example 3 Exactly as stated in Example 3, a homogeneous mixture is produced, but instead of 4% 4,4'-bis (N- ⁇ -hydroxyethyl-N-methylamino) benzophenone, 4% 4,4'-bis (N-dimethyl -amino) benzophenone used. The mixture is stored exactly as that of Example 3 for 3 months at room temperature. At this point it shows a cloudiness due to fine crystals of 4,4'-bis (N-dimethylamino) benzophenone.
- One UV-curing binder mixture each from 30% of an LJ Urethane acrylate (made by reacting an aliphatic biuret isocyanate with stoichiometric amounts of hydroxypropyl acrylate), 54% of another urethane acrylate (made by reacting hexamethylene diisocyanate with stoichiometric amounts of hydroxypropyl acrylate), 10% N ', N'-divinyl-2-oxo-hexahydropyrimidine, 3 % Benzophenone and 3% 4,4'-bis (N- ⁇ -hydroxyethyl-N-methylamino) benzophenone (Example 4) and 3% Michler's ketone (comparative experiment C) is separated using a test printer in a layer thickness of about 1 , 3 / um printed on art paper.
- the printed layers produced from the various binder mixtures are irradiated on a commercially available UV curing system, containing 2 medium pressure mercury lamps, each with an output of 80 watt / cm arc length, and the maximum conveyor belt speed is determined, at which only one lamp has an immediate, tack-free one when switched on and abrasion-resistant curing of the printed layer can be achieved.
- the printing ink of comparative test D After 2 weeks of storage, the printing ink of comparative test D has a matt, granular surface. Fine crystals of Michler's ketone can be seen under the microscope.
- the color prints are irradiated as described in Example 4 (but both lamps are switched on) and the maximum conveyor belt speed is determined, which is
Abstract
Photopolymerisierbare Bindemittel für Druckfarben, Überzüge und Druckplatten auf der Basis von olefinisch ungesättigten Verbindungen und gegebenenfalls einer polymeren Bindemittelkomponente, enthaltend eine Diaminobenzophenon-Verbindung als Photosensibilisator, werden in ihren toxischen Eigenschaften sowie bezüglich ihrer Lagerstabilität dadurch verbessert, dass sie als Diaminobenzophenon-Verbindung eine solche der Formel R¹R²N-C6H4-CO-C6H4-NR³R<4> enthalten, worin R¹ und R³ H(OR<5>)x-Reste mit R<5> = Alkylen mit 2 bis 3 C-Atomen und x = 1, 2 oder 3, R² und R<4> Alkylreste mit 1 bis 4 C-Atomen oder Reste der für R¹ und R³ genannten Art darstellen.Photopolymerizable binders for printing inks, coatings and printing plates based on olefinically unsaturated compounds and optionally a polymeric binder component containing a diaminobenzophenone compound as a photosensitizer are improved in their toxic properties and in terms of their storage stability by virtue of being a diaminobenzophenone compound Formula R¹R²N-C6H4-CO-C6H4-NR³R <4> contain, wherein R¹ and R³ H (OR <5>) x radicals with R <5> = alkylene with 2 to 3 carbon atoms and x = 1, 2 or 3, R² and R <4> represent alkyl radicals having 1 to 4 carbon atoms or radicals of the type mentioned for R¹ and R³.
Description
Die Erfindung betrifft photopolymerisierbare Bindemittel für Druckfarben, Überzüge und Druckplatten auf der Basis mindestens einer photopolymerisierbaren olefinisch ungesättigten Verbindung sowie gegebenenfalls einer polymeren Bindemittelkomponente, die eine vorteilhafte Diaminobenzophenon-Verbindung als Photosensibilisator enthalten.The invention relates to photopolymerizable binders for printing inks, coatings and printing plates based on at least one photopolymerizable olefinically unsaturated compound and optionally a polymeric binder component which contain an advantageous diaminobenzophenone compound as a photosensitizer.
Aminogruppenhaltige Benzophenonderivate sind bekannt. Besonders vielfach ist 4,4'-Bis(N-dimethylamino)benzophenon (Michlers Keton) und seine Anwendung in Photoinitiator-Systemen oder als Photosensibilisator für photopolymerisierbare Systeme beschrieben (vgl. DT-OS 15 22 359). Es ist ein Nachteil von Michlers Keton, daß seine toxischen Eigenschaften für manche Anwendungszzwecke nicht befriedigen, ferner,seine begrenzte Löslichkeit in vielen organischen Lösungsmitteln und seine begrenzte Verträglichkeit mit manchen polaren photopolymerisierbaren Bindemitteln zu wünschen übrig läßt, wodurch bei Erfordernis höherer Konzentrationen an Photosensibilisatoren leicht Trübungen in den entsprechenden Gemischen auftreten, die eine Photopolymerisation störend beeinflussen.Benzophenone derivatives containing amino groups are known. 4,4'-bis (N-dimethylamino) benzophenone (Michler's ketone) and its use in photoinitiator systems or as a photosensitizer for photopolymerizable systems have been described particularly frequently (cf. DT-OS 15 22 359). It is a disadvantage of Michler's ketone that its toxic properties are unsatisfactory for some applications, further that its limited solubility in many organic solvents and its limited compatibility with some polar photopolymerizable binders leave something to be desired, which, if higher concentrations of photosensitizers are required, can easily cause clouding occur in the corresponding mixtures, which interfere with photopolymerization.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, für photopolymerisierbare Bindemittel einen Ersatz für Michlers Keton zu finden, der verbesserte toxische Eigenschaften, eine verbesserte Verträglichkeit mit photopolymerisierbaren Gemischen aufweist und eine vielseitige Verwendung als Photosensibilisator bzw. Komponente in Photoinitiator-Systemen für photopolymerisierbare Massen gestattet.The object of the present invention was to find a substitute for Michler's ketone for photopolymerizable binders, which has improved toxic properties, an improved compatibility with photopolymerizable mixtures and allows a versatile use as a photosensitizer or component in photoinitiator systems for photopolymerizable compositions.
Es wurde nun gefunden, daß photopolymerisierbare Bindemittel für Druckfarben, Überzüge und Druckplatten auf der Basis mindestens einer photopolymerisierbaren olefinisch ungesättigten Verbindung sowie gegebenenfalls einer polymeren Bindemittelkomponente, die eine Diaminobenzophenon-Verbindung als Photosensibilisator enthalten, die gewünschten verbesserten Eigenschaften zeigen, wenn sie eine Diaminobenzophenon-Verbindung der Formel (I)
Beispiele solcher Verbindungen sind 4,4'-Bis (N-ß-hydroxyäthyl-N-methylamino)benzophenon, 4,4'-Bis(N-ß-hydroxyäthyl-N-äthyl-amino)-benzophenon, 4,4'-Bis(N-β-hydroxyäthyl-N-propyl-amino)benzophenon, 4,4'-Bis(N-β-hydroxypropyl-N-methyl-amino)benzophenon, 4,4'-Bis-(N-hydroxypropyl-N-methyl-amino)benzophenon, 4,4'-Bis(N-hydroxyäthoxyäthyl-N-methyl-amino)benzophenon der Formel (II)
Sehr geeignet sind die 4,4'-Bis(N-hydroxyäthyl-N-C1-C4- alkyl-amino)benzophenone.The 4,4'-bis (N-hydroxyethyl-NC 1 -C 4 -alkyl-amino) benzophenones are very suitable.
Einen technisch einfachen Weg zur Herstellung von N-Hydroxyalkylaminoderivate des Benzophenons stellt die folgende Umsetzung dar:
Durch Einsatz von Gemischen verschiedener N-Hydroxyalkyl-N-alkyl-aniline bzw. N,N-Dihydroxyalkylaniline, für die Umsetzung mit Formaldehyd bzw. Paraformaldehyd in Gegenwart von Säure lassen sich auch unsymmetrische Derivate des Di- aminobenzophenons herstellen, wobei als Zwischenprodukte stets die entsprechend substituierten Diaminodiphenylmethane entstehen, die dann durch Oxidation mit Sauerstoff z.B. in Gegenwart von Chlcranil und Eisenkomplexen des Dihydrodibenzotetraaza-annulens in die entsprechend substituierten Diaminobenzophenone. umgewandelt werden können. Die erfindungsgemäß als Photosensibilisatoren verwendeten Verbindungen lassen sich dann leicht als meist nadelförmig kristalline feste Substanzen mit Schmelzpunkten über 100°C isolieren und reinigen.By using mixtures of different N-hydroxyalkyl-N-alkyl-anilines or N, N-dihydroxyalkylanilines, for the reaction with formaldehyde or paraformaldehyde in the presence of acid, asymmetrical derivatives of di- produce aminobenzophenones, the intermediates always resulting in the correspondingly substituted diaminodiphenylmethanes, which are then oxidized with oxygen, for example in the presence of chloranil and iron complexes of dihydrodibenzotetraaza annulene, into the appropriately substituted diaminobenzophenones. can be converted. The compounds used as photosensitizers according to the invention can then be easily isolated and purified as mostly acicular crystalline solid substances with melting points above 100 ° C.
Die erfindungsgemäß in photopolymerisierbaren Bindemitteln verwendeten Diaminobenzophenon-Verbindungen weisen bei mit Michlers Keton vergleichbarer Aktivität als Photosensibilisator die Vorteile auf, daß sie weniger toxisch als Michlers Keton sind, in vielen organischen Lösungsmitteln eine bessere Löslichkeit und mit vielen polaren photopolymeri-. sierbaren Gemischen eine verbesserte Verträglichkeit auf-. weisen.The diaminobenzophenone compounds used according to the invention in photopolymerizable binders have, with activity comparable to Michler's ketone as photosensitizer, the advantages that they are less toxic than Michler's ketone, better solubility in many organic solvents and with many polar photopolymeric. Mixtures that can be improved. point.
Von besonderem Vorteil ist es, im erfindungsgemäßen Bindemittel neben der Diaminobenzophenon-Verbindung einen weiteren bekannten Photoaktivator mitzuverwenden, wie Benzoin, Benzoinäther, Anthrachinon, Benzil, Benzilmonoalkylketale, Fluorenon, Fluoren, Diacetyl und insbesondere Benzophenon oder ein im Bereich von 300 bis 380 nm niedrig absorbierendes Benzophenonäerivat, wie solchen mit einem Extinktionskoeffizienten ε360. nm < 200, wobei die für die Kombination mit Michlers Keton bekannten molaren Verhältnisse und Mengen angewandt werden können.It is particularly advantageous to use, in addition to the diaminobenzophenone compound, a further known photoactivator in the binder according to the invention, such as benzoin, benzoin ether, anthraquinone, benzil, benzil monoalkyl ketals, fluorenone, fluorene, diacetyl and in particular benzophenone or a low absorbent in the range from 300 to 380 nm Benzophenone derivative, such as those with an extinction coefficient ε 360 nm <200, it being possible to use the molar ratios and amounts known for the combination with Michler's ketone.
Als photopolymerisierbare olefinisch ungesättigten Verbindungen kommen die bekannten niedrigmolekularen Monomeren und Oligomeren (insbesondere mit einem Molekulargewicht unter 2 000) in Frage, die für photopolymerisierbare Binde- mittel für Druckfarben, Überzugsmittel und für Druckplatten? an sich bekannt sind, wobei sich natürlich die Art der Monomeren nach dem Anwendungszweck richtet und nach dem gegebenenfalls mitverwendeten polymeren Bindemittel, mit dem sie verträglich sein sollen. Bevorzugt sind Monomere mit zwei- oder mehr olefinisch ungesättigten photopolymerisierbaren Doppelbindungen allein oder deren Mischungen mit Monomeren mit nur einer olefinisch ungesättigten photopolymerisierbaren Doppelbindung, wobei der Anteil der Monomeren mit nur einer Doppelbindung im allgemeinen nur etwa 5 bis 50 und bevorzugt 5 bis 30 Gewichtsprozent der Gesamtmonomerenmenge beträgt.Suitable photopolymerizable olefinically unsaturated compounds are the known low molecular weight monomers and oligomers (in particular with a molecular weight below 2,000) which are suitable for photopolymerizable binders. medium for printing inks, coating agents and for printing plates? are known per se, the nature of the monomers, of course, depending on the intended use and on the polymer binder which may be used, with which they should be compatible. Monomers with two or more olefinically unsaturated photopolymerizable double bonds alone or mixtures thereof with monomers with only one olefinically unsaturated photopolymerizable double bond are preferred, the proportion of monomers with only one double bond generally only being about 5 to 50 and preferably 5 to 30 percent by weight of the total amount of monomers is.
Geeignete olefinisch ungesättigte Verbindungen sind Di- und Polyacrylate und -methacrylate, wie sie durch Veresterung von Diolen oder Polyolen mit Acrylsäure oder Methacrylsäure hergestellt werden können, wie die Di- und Tri(meth)acrylate von Äthylenglykol, Diäthylenglykol, Triäthylenglykol, Polyäthylenglykol mit einem Molekulargewicht bis etwa 500, 1,2-Propandiol, 1,3-Propandiol, Neopentylglykol (2,2-Dlmethylpropandiol) 1,4-Butandiol, 1,1,1-Trimethylolpropan, Glycerin oder Pentaerithrit; ferner die Monoacrylate und Monomethacrylate solcher Diole und Polyole, wie z.B. Äthylenglykol- oder Di-, Tri- oder Tetraäthylenglykolmonoacrylat, Monomere mit zwei- oder mehr olefinisch ungesättigten Bindungen, die Urethangruppen und/oder Amidgruppen enthalten, wie die aus aliphatischen Diolen der vorstehend genannten Art, organischen Diisocyanaten und Hydroxyalkyl(meth)acrylaten hergestellten niedermolekularen Verbindungen. Genannt seien auch Acrylsäure, Methacrylsäure sowie deren Derivate wie (Meth)acrylamid, N-Hydroxymethyl(meth)-acrylamid oder (Meth)acrylate von Monoalkoholen mit 1 bis 6 C-Atomen.Suitable olefinically unsaturated compounds are di- and polyacrylates and methacrylates, as can be prepared by esterification of diols or polyols with acrylic acid or methacrylic acid, such as the di- and tri (meth) acrylates of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol with a molecular weight up to about 500, 1,2-propanediol, 1,3-propanediol, neopentyl glycol (2,2-dimethyl propanediol) 1,4-butanediol, 1,1,1-trimethylol propane, glycerol or pentaerythritol; furthermore the monoacrylates and monomethacrylates of such diols and polyols, e.g. Ethylene glycol or di-, tri- or tetraethylene glycol monoacrylate, monomers with two or more olefinically unsaturated bonds containing urethane groups and / or amide groups, such as the low molecular weight compounds prepared from aliphatic diols of the type mentioned above, organic diisocyanates and hydroxyalkyl (meth) acrylates . Also mentioned are acrylic acid, methacrylic acid and their derivatives such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide or (meth) acrylates of monoalcohols with 1 to 6 carbon atoms.
Sehr gewährt haben sich erfindungsgemäße Bindemittel, die polare Monomere und/oder polare polymere Bindemittel enthalten., wie Urethanacrylate oder Epoxidacrylate. Bezüglich geeigneter Bindemittelkomponenten sowie der Anwendung der erfindungsgemäßen Systeme sei auf die DT-OS 1 522 359, 2 200 478, 2 358 948, 2 441 148 verwiesen, wobei die erfindungsgemäß verwendeten Diaminobenzophenon-Verbindungen an die Stelle des dort beschriebenen Michlers Keton treten können.Binders according to the invention which contain polar monomers and / or polar polymeric binders, such as urethane acrylates or epoxy acrylates, have been very successful. With regard to suitable binder components and the use of the systems according to the invention, reference is made to DT-OS 1 522 359, 2 200 478, 2 358 948, 2 441 148, the diaminobenzophenone compounds used according to the invention being able to replace the Michler ketone described there.
Geeignete polymere Bindemittelkomponenten sind z.B. Polyamide, Polyurethane, ungesättigte Polyester sowie Polyesterurethane. In bekannter Weise können die erfindungsgemäßen photopolymerisierbaren Bindemittel mit den üblichen Zusätzen vermischt werden, wie thermischen Polymerisationsinhibitoren, Farbstoffen, Weichmachern usw.Suitable polymeric binder components are e.g. Polyamides, polyurethanes, unsaturated polyesters and polyester urethanes. The photopolymerizable binders according to the invention can be mixed in a known manner with the usual additives, such as thermal polymerization inhibitors, dyes, plasticizers, etc.
Besondere Bedeutung kommt .der größeren Löslichkeit der erfindungsgemäß angewendeten Photosensibilisatoren bei ihrer Verwendung für eine ausreichende Härtung hoch pigmentierter photopolymerisierbarer Systeme zu, insbesondere bei Verwendung hochabsorbierender Pigmente, z.B. in UV-härtenden Druckfarben mit deckendem Schwarz. Gemäß Beispielen 5 und 6 zeigen die hierbei erzielten Drucke eine stark verbesserte Brillanz. Die erfindungsgemäßen Bindemittel eignen sich besonders in Schichtdicken kleiner als 10/um für UV-härtende Druckfarben, aber auch für Offsetdruckplattenbeschichtungen und als Photoresist-Material.Of particular importance is the greater solubility of the photosensitizers used according to the invention when they are used for adequate curing of highly pigmented photopolymerizable systems, in particular when using highly absorbent pigments, for example in UV-curing printing inks with opaque black. According to Examples 5 and 6, the prints achieved here show a greatly improved brilliance. The binders of the invention are particularly suitable less than 10 / um for UV-curing printing inks, but also for offset printing plate coatings and as a photoresist material in layer thicknesses.
Die in den nachstehenden Beispielen und Vergleichsversuchen genannten Teile und Prozente beziehen sich, soweit nicht anders angegeben, auf das Gewicht.The parts and percentages given in the examples and comparative tests below relate to the weight, unless stated otherwise.
Eine Mischung aus 151 Teilen N-Methyl-N-hydroxyäthylanilin, 16,5 Teilen Paraformaldehyd und 100 Teilen Eisessig wird 1,5 Stunden auf 60 bis 70°C erhitzt. Nach Zugabe von 230 Teilen Methanol, 25 Teilen Chloranil und 2,5 Teilen des Eisenkomplexes des Dihydrodibenzotetraazaannulens zu der Kondensationslösung wird diese bei 50 bis 52°C und 1 bis 3 bar mit Luft behandelt. Die Oxidation wird abgebrochen, wenn fast kein Sauerstoff mehr aufgenommen wird. Aus der auf 10°C abgekühlten Reaktionsmischung kristallisieren farblose Nadeln aus, die abgesaugt und mit 190 Teilen Methanol gewaschen werden. Nach Umkristallisieren aus Methanol werden 885 Teile 4,4'-Bis(N-methyl-N-hydroxyäthyl- amino)benzophenon erhalten mit einem Schmelzpunkt von 153°C.A mixture of 151 parts of N-methyl-N-hydroxyethylaniline, 16.5 parts of paraformaldehyde and 100 parts of glacial acetic acid is heated to 60 to 70 ° C for 1.5 hours. After adding 230 parts of methanol, 25 parts of chloranil and 2.5 parts of the iron complex of dihydrodibenzotetraazaannulene to the condensation solution, the latter is treated with air at 50 to 52 ° C. and 1 to 3 bar. The oxidation is stopped when almost no more oxygen is taken up. Colorless needles crystallize out of the reaction mixture, which has cooled to 10 ° C., and are filtered off with suction and washed with 190 parts of methanol. After recrystallization from methanol, 885 parts of 4,4'-bis (N-methyl-N-hydroxyethylamino) benzophenone are obtained with a melting point of 153 ° C.
Durch homogenes Vermischen der Komponenten bei 90 bis 100°C wird ein UV-härtbares Bindemittel hergestellt, bestehend aus 20 % eines Urethanacrylats (hergestellt durch Umsetzung eines aliphatischen Biuretisocyanats mit stöchiometrischen Mengen an Hydroxypropylacrylat), 64 % eines weiteren Urethanacrylats (hergestellt durch Umsetzung von Hexamethylendiisocyanat mit stöchiometrischen Mengen an Hydroxypropylacrylat), 10 % Butandiol-diglycidyläther-diacrylat, 3 % Benzophenon und 3 % 4,4'-Bis(N-ß-hydroxyäthyl-N-methylamino) benzophenon.A UV-curable binder is produced by homogeneously mixing the components at 90 to 100 ° C, consisting of 20% of a urethane acrylate (produced by reacting an aliphatic biuret isocyanate with stoichiometric amounts of hydroxypropyl acrylate), 64% of a further urethane acrylate (produced by reacting hexamethylene diisocyanate) with stoichiometric amounts of hydroxypropyl acrylate), 10% butanediol diglycidyl ether diacrylate, 3% benzophenone and 3% 4,4'-bis (N-ß-hydroxyethyl-N-methylamino) benzophenone.
Das UV-härtbare Bindemittel ist auch nach 3 monatiger Lagerung bei Raumtemperatur klar.The UV-curable binder is clear even after 3 months of storage at room temperature.
Genau wie in Beispiel 2 angegeben wird ein UV-härtbares Bindemittel hergestellt, jedoch anstelle von 3 % 4,4'-Bis (N-ß-hydroxyäthyl-N-methyl-amino)benzophenon wird 3 % 4,4'-Bis(N-dimethylamino)benzophenon verwendet. Das Bindemittel wird exakt wie jenes von Beispiel 2 etwa 3 Monate lang bei Raumtemperatur gelagert, zeigt dann jedoch eine deutliche Trübung durch feine Kristalle.A UV-curable binder is produced exactly as stated in Example 2, but instead of 3% 4,4'-bis (N-β-hydroxyethyl-N-methylamino) benzophenone, 3% 4,4'-bis (N -dimethylamino) benzophenone used. The binder is stored exactly like that of Example 2 for about 3 months at room temperature, but then shows a clear cloudiness due to fine crystals.
Ein homogenes Gemisch aus 52 % eines Epoxidharz-Acrylats (hergestellt durch Umsetzung eines Bisphenol A-Epichlorhydrin-Harzes mit einem Epoxid-Äquivalentgewicht von 190 mit 97 Mol%, bezogen auf die.Epoxidgruppen, reiner Acrylsäure), 40 % Pentaerythrittetraacrylat, 4 % Bezophenon und 4 % 4,4'-Bis(N-β-Hydroxyäthyl-N-methyl-amino)benzophenon wird 3 Monate'bei Raumtemperatur gelagert. Die Mischung bleibt klar und ungetrübt.A homogeneous mixture of 52% of an epoxy resin acrylate (produced by reacting a bisphenol A epichlorohydrin resin with an epoxy equivalent weight of 190 with 97 mol%, based on the epoxy groups, pure acrylic acid), 40% pentaerythritol tetraacrylate, 4% bezophenone and 4% 4,4'-bis (N-β-hydroxyethyl-N-methylamino) benzophenone is stored for 3 months at room temperature. The mixture remains clear and unclouded.
Genau wie in Beispiel 3 angegeben wird ein homogenes Gemisch hergestellt, jedoch anstelle von 4 % 4,4'-Bis(N-ß- hydroxyäthyl-N-methyl-amino)benzophenon wird 4 % 4,4'-Bis (N-dimethyl-amino)benzophenon verwendet. Das Gemisch wird exakt wie jenes von Beispiel 3 3 Monate lang bei Raumtemperatur gelagert. Es zeigt zu diesem Zeitpunkt eine Trübung durch feine Kristalle von 4,4'-Bis(N-dimethyl- amino)benzophenon.Exactly as stated in Example 3, a homogeneous mixture is produced, but instead of 4% 4,4'-bis (N-β-hydroxyethyl-N-methylamino) benzophenone, 4% 4,4'-bis (N-dimethyl -amino) benzophenone used. The mixture is stored exactly as that of Example 3 for 3 months at room temperature. At this point it shows a cloudiness due to fine crystals of 4,4'-bis (N-dimethylamino) benzophenone.
Je ein UV-härtendes Bindemittelgemisch aus 30 % eines L J Urethanacrylats (hergestellt durch Umsetzung eines aliphatischen Biuretisocyanats mit stöchiometrischen Mengen an Hydroxypropylacrylat), 54 % eines weiteren Urethanacrylats (hergestellt durch Umsetzung von Hexamethylendiisocyanat mit stöchiometrischen Mengen an Hydroxypropylacrylat), 10 % N',N'-Divinyl-2-oxo-hexahydropyrimidin, 3 % Benzophenon und 3 % 4,4'-Bis(N-ß-hydroxyäthyl-N-methyl-amino) benzophenon (Beispiel 4) bzw. 3 % Michlers Keton (Vergleichsversuch C) wird getrennt mittels eines Probedruckgerätes in einer Schichtdicke von etwa 1,3/um auf Kunstdruckpapier aufgedruckt. Die aus den verschiedenen Bindemittelgemischen hergestellten aufgedruckten Schichten werden auf einer handelsüblichen UV-Härtungsanlage, enthaltend 2 Quecksilbermitteldrucklampen mit je einer Leistung von 80 Watt/cm Bogenlänge bestrahlt, und es wird die maximale Transportbandgeschwindigkeit bestimmt, bei der bei Einschalten nur einer Lampe noch eine sofortige klebfreie und abriebfeste Härtung der aufgedruckten Schicht erzielt werden kann.One UV-curing binder mixture each from 30% of an LJ Urethane acrylate (made by reacting an aliphatic biuret isocyanate with stoichiometric amounts of hydroxypropyl acrylate), 54% of another urethane acrylate (made by reacting hexamethylene diisocyanate with stoichiometric amounts of hydroxypropyl acrylate), 10% N ', N'-divinyl-2-oxo-hexahydropyrimidine, 3 % Benzophenone and 3% 4,4'-bis (N-β-hydroxyethyl-N-methylamino) benzophenone (Example 4) and 3% Michler's ketone (comparative experiment C) is separated using a test printer in a layer thickness of about 1 , 3 / um printed on art paper. The printed layers produced from the various binder mixtures are irradiated on a commercially available UV curing system, containing 2 medium pressure mercury lamps, each with an output of 80 watt / cm arc length, and the maximum conveyor belt speed is determined, at which only one lamp has an immediate, tack-free one when switched on and abrasion-resistant curing of the printed layer can be achieved.
Ergebnis max. Bandgeschwindigkeit: Beispiel 4: 280 m/min Vergleichsvers. C: 280 m/minResult max. Belt speed: Example 4: 280 m / min comparative vers. C: 280 m / min
Die Druckfarbe des Vergleichsversuches D weist nach 2-wöchiger Lagerung eine mattere, körnige Oberfläche auf. Unter dem Mikroskop sind feine Kristalle von Michlers Keton erkennbar.After 2 weeks of storage, the printing ink of comparative test D has a matt, granular surface. Fine crystals of Michler's ketone can be seen under the microscope.
UV-härtende Druckfarben und mit ihnen Farbdrucke auf Kunst-' druckpapier mit einer optischen Dichte von 2,0 bis 2,1 hergestellt. Die Farbdrucke werden wie in Beispiel 4 beschrieben (jedoch sind beide Lampen eingeschaltet) bestrahlt und die maximale Transportbandgeschwindigkeit bestimmt, die beträgt
Auch hier zeigte die Probe des Vergleichsversuchs E nach 2-wöchiger Lagerung infolge einer Kristallisation von Michlers Keton eine mattere Oberfläche.Here too, the sample from comparative experiment E showed a matt surface after 2 weeks' storage as a result of crystallization of Michler's ketone.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772730897 DE2730897A1 (en) | 1977-07-08 | 1977-07-08 | PHOTOPOLYMERIZABLE BINDERS |
| DE2730897 | 1977-07-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000342A1 true EP0000342A1 (en) | 1979-01-24 |
| EP0000342B1 EP0000342B1 (en) | 1981-11-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100236A Expired EP0000342B1 (en) | 1977-07-08 | 1978-06-26 | Photopolymerisable binders |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4147604A (en) |
| EP (1) | EP0000342B1 (en) |
| JP (1) | JPS5417987A (en) |
| AT (1) | AT370756B (en) |
| DE (2) | DE2730897A1 (en) |
| IT (1) | IT1105066B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2132212A (en) * | 1982-10-28 | 1984-07-04 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| EP0755949A1 (en) * | 1995-07-22 | 1997-01-29 | Basf Aktiengesellschaft | Radiation curable masses containing covalently bonded photoinitiators |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4576975A (en) * | 1983-03-03 | 1986-03-18 | Minnesota Mining And Manufacturing Company | Water soluble Michler's ketone analogs in combined photoinitiator composition and polymerizable composition |
| US4507497A (en) * | 1983-03-03 | 1985-03-26 | Minnesota Mining And Manufacturing Company | Water soluble michlers ketone analogs |
| US4563438A (en) * | 1983-05-06 | 1986-01-07 | Ciba Geigy Corporation | Liquid mixture of photoinitiators |
| US4532021A (en) * | 1983-07-18 | 1985-07-30 | Desoto, Inc. | Adherent ultraviolet cured coatings |
| DE3331474A1 (en) * | 1983-09-01 | 1985-03-21 | Basf Ag, 6700 Ludwigshafen | PHOTOPOLYMERIZABLE MIXTURES WITH SPECIAL DIAMINOBENZOPHENONE COMPOUNDS |
| US4565769A (en) * | 1984-11-21 | 1986-01-21 | E. I. Du Pont De Nemours And Company | Polymeric sensitizers for photopolymer composition |
| GB2410499A (en) * | 2004-01-29 | 2005-08-03 | Sun Chemical Ltd | Piperazino photoinitiation sensitisers |
| TWI337575B (en) * | 2005-03-25 | 2011-02-21 | Daido Kogyo Kk | Paper cutting machine having rest |
| CN107567466B (en) | 2015-01-05 | 2020-10-09 | Igm集团公司 | LED curable low mobility photoinitiators |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933682A (en) * | 1973-01-31 | 1976-01-20 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
| US3966573A (en) * | 1974-10-31 | 1976-06-29 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
| GB1486911A (en) * | 1974-09-17 | 1977-09-28 | Scm Corp | Ultraviolet and laser curing of polymerizable binders |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337902B2 (en) * | 1973-09-04 | 1978-10-12 | ||
| US4056453A (en) * | 1973-11-27 | 1977-11-01 | Basf Aktiengesellschaft | Uv-curing printing inks |
| GB1486411A (en) | 1974-09-11 | 1977-09-21 | Peel E | Flat plate coolers |
| JPS591401B2 (en) * | 1976-04-26 | 1984-01-12 | 東洋インキ製造株式会社 | UV curable composition |
| US4048034A (en) * | 1976-08-27 | 1977-09-13 | Uop Inc. | Photopolymerization using an alpha-aminoacetophenone |
-
1977
- 1977-07-08 DE DE19772730897 patent/DE2730897A1/en not_active Withdrawn
-
1978
- 1978-06-26 EP EP78100236A patent/EP0000342B1/en not_active Expired
- 1978-06-26 DE DE7878100236T patent/DE2861345D1/en not_active Expired
- 1978-06-27 IT IT50047/78A patent/IT1105066B/en active
- 1978-07-03 US US05/921,468 patent/US4147604A/en not_active Expired - Lifetime
- 1978-07-07 AT AT0495078A patent/AT370756B/en not_active IP Right Cessation
- 1978-07-08 JP JP8252478A patent/JPS5417987A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933682A (en) * | 1973-01-31 | 1976-01-20 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
| GB1486911A (en) * | 1974-09-17 | 1977-09-28 | Scm Corp | Ultraviolet and laser curing of polymerizable binders |
| US3966573A (en) * | 1974-10-31 | 1976-06-29 | Sun Chemical Corporation | Photopolymerization co-initiator systems |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2132212A (en) * | 1982-10-28 | 1984-07-04 | Fuji Photo Film Co Ltd | Photopolymerizable composition |
| EP0755949A1 (en) * | 1995-07-22 | 1997-01-29 | Basf Aktiengesellschaft | Radiation curable masses containing covalently bonded photoinitiators |
| US5859084A (en) * | 1995-07-22 | 1999-01-12 | Basf Aktiengesellschaft | Radiation-curable compositions containing photoinitiators linked by a covalent bond |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2730897A1 (en) | 1979-02-01 |
| US4147604A (en) | 1979-04-03 |
| IT1105066B (en) | 1985-10-28 |
| JPS5417987A (en) | 1979-02-09 |
| ATA495078A (en) | 1982-09-15 |
| AT370756B (en) | 1983-05-10 |
| IT7850047A0 (en) | 1978-06-27 |
| DE2861345D1 (en) | 1982-01-28 |
| JPS6331483B2 (en) | 1988-06-24 |
| EP0000342B1 (en) | 1981-11-25 |
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