EP0000342B1 - Photopolymerisierbare Bindemittel - Google Patents

Photopolymerisierbare Bindemittel Download PDF

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Publication number
EP0000342B1
EP0000342B1 EP78100236A EP78100236A EP0000342B1 EP 0000342 B1 EP0000342 B1 EP 0000342B1 EP 78100236 A EP78100236 A EP 78100236A EP 78100236 A EP78100236 A EP 78100236A EP 0000342 B1 EP0000342 B1 EP 0000342B1
Authority
EP
European Patent Office
Prior art keywords
benzophenone
photopolymerizable
bis
binder
binders
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.)
Expired
Application number
EP78100236A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000342A1 (de
Inventor
Werner Dr. Kuesters
Guenter Dr. Heil
Martin Dr. Fischer
Manfred Dr. Eisert
Hellmut Dr. Kast
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0000342A1 publication Critical patent/EP0000342A1/de
Application granted granted Critical
Publication of EP0000342B1 publication Critical patent/EP0000342B1/de
Expired legal-status Critical Current

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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 has 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 in the corresponding mixtures occur that 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-ß-hydroxyethyl-N-propylamino) benzophenone, 4,4'-bis (N-ß-hydroxypropyl-N-methylamino) benzophenone, 4,4'-bis (N-hydroxypropyl- N-methylamino) benzophenone, 4,4'-bis (N-hydroxyethoxyethyl-N-methylamino) benzophenone of the formula (11) further 4,4'-bis (N, N-dihydroxyalkylamino) benzophenones such as 4,4-bis (N, N-di- ⁇ -hydroxyethylamino) benzophenone, 4,4'-bis (N, N -di-ß-hydroxypropylamino)
  • asymmetrical derivatives of diaminobenzophenone can also be prepared, the correspondingly substituted ones always being intermediates Diaminophenylmethane arise, which then by oxidation with oxygen, for example can be converted into the correspondingly substituted diaminobenzophenones in the presence of chloranil and iron complexes of dihydrodibenzotetraaza annulene.
  • 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.
  • 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, have better solubility in many organic solvents and have better compatibility with many polar photopolymerizable mixtures.
  • 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 E360. nm ⁇ 200, whereby the molar ratios and amounts known for the combination with Michler's ketone can be used.
  • 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 known per se for photopolymerizable binders for printing inks, coating agents and for printing plates, the nature of the monomers, of course, depending on the intended use depends and, if necessary, also used polymeric binder 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-dimethylpropanediol) 1,4-butanediol, 1,1,1-trimethylolpropane, glycerin 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 which contain urethane groups and / or amide groups, such as those of low molecular weight prepared from aliphatic diols of the aforementioned type, organic diisocyanates and hydroxyalkyl (meth) acrylates Links.
  • 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 proven very useful. 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.
  • Suitable polymeric binder components are, for example, polyamides, polyurethanes, unsaturated polyesters and polyester urethanes.
  • the inventive photopolymerizable binders can be mixed with the usual additives, such as thermal polymerization inhibitors, dyes, plasticizers, etc.
  • the binders according to the invention are particularly suitable in layer thicknesses of less than 10 ⁇ m for UV-curing printing inks, but also for offset printing plate coatings and as a photoresist material.
  • 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 1, 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 1 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% benzophenone 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 2 Exactly as stated in Example 2, 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 like that of Example 2 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 a urethane acrylate (produced by reaction of an aliphatic biuret isocyanate with stoichiometric amounts of hydroxypropyl acrylate), 54% of a further urethane acrylate (produced by reaction of 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 3) or 3% 4,4'- Bis (N-dimethylamino) benzophenone (comparative experiment C) is printed separately on a test paper in a layer thickness of about 1.3 ⁇ m 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 watts / cm arc length, and the maximum conveyor belt speed is determined, at which only one lamp has an immediate non-tacky 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 4,4'-bis (N-dimethylamino) benzophenone) can be seen under the microscope.
  • the color prints are irradiated as described in Example 3 (but both lamps are switched on) and the maximum conveyor belt speed is determined, which is.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Polymerisation Methods In General (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
EP78100236A 1977-07-08 1978-06-26 Photopolymerisierbare Bindemittel Expired EP0000342B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2730897 1977-07-08
DE19772730897 DE2730897A1 (de) 1977-07-08 1977-07-08 Photopolymerisierbare bindemittel

Publications (2)

Publication Number Publication Date
EP0000342A1 EP0000342A1 (de) 1979-01-24
EP0000342B1 true EP0000342B1 (de) 1981-11-25

Family

ID=6013462

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100236A Expired EP0000342B1 (de) 1977-07-08 1978-06-26 Photopolymerisierbare Bindemittel

Country Status (6)

Country Link
US (1) US4147604A (enExample)
EP (1) EP0000342B1 (enExample)
JP (1) JPS5417987A (enExample)
AT (1) AT370756B (enExample)
DE (2) DE2730897A1 (enExample)
IT (1) IT1105066B (enExample)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5978339A (ja) * 1982-10-28 1984-05-07 Fuji Photo Film Co Ltd 光重合性組成物
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 (de) * 1983-09-01 1985-03-21 Basf Ag, 6700 Ludwigshafen Photopolymerisierbare mischungen mit speziellen diaminobenzophenon-verbindungen
US4565769A (en) * 1984-11-21 1986-01-21 E. I. Du Pont De Nemours And Company Polymeric sensitizers for photopolymer composition
DE19526856A1 (de) * 1995-07-22 1997-01-23 Basf Ag Strahlungshärtbare Massen mit kovalent gebundenen Photoinitiatoren
GB2410499A (en) * 2004-01-29 2005-08-03 Sun Chemical Ltd Piperazino photoinitiation sensitisers
EP3798238A1 (en) 2015-01-05 2021-03-31 IGM Group B.V. Led-curable low migration photoinitiators
CN119708499A (zh) * 2023-09-28 2025-03-28 上海交通大学 低表面能大分子光引发剂、uv led光固化涂料及光固化肤感涂层
CN117343262A (zh) * 2023-10-31 2024-01-05 清华大学 一种紫外光照调控力学性能的聚氨酯脲薄膜及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933682A (en) * 1973-01-31 1976-01-20 Sun Chemical Corporation Photopolymerization co-initiator systems
JPS5337902B2 (enExample) * 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
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
JPS591401B2 (ja) * 1976-04-26 1984-01-12 東洋インキ製造株式会社 紫外線硬化性組成物
US4048034A (en) * 1976-08-27 1977-09-13 Uop Inc. Photopolymerization using an alpha-aminoacetophenone

Also Published As

Publication number Publication date
AT370756B (de) 1983-05-10
DE2861345D1 (de) 1982-01-28
JPS5417987A (en) 1979-02-09
US4147604A (en) 1979-04-03
DE2730897A1 (de) 1979-02-01
IT7850047A0 (it) 1978-06-27
JPS6331483B2 (enExample) 1988-06-24
ATA495078A (de) 1982-09-15
EP0000342A1 (de) 1979-01-24
IT1105066B (it) 1985-10-28

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