EP2276816A1 - Strahlenhärtbare druckfarbe oder drucklack - Google Patents

Strahlenhärtbare druckfarbe oder drucklack

Info

Publication number
EP2276816A1
EP2276816A1 EP09745549A EP09745549A EP2276816A1 EP 2276816 A1 EP2276816 A1 EP 2276816A1 EP 09745549 A EP09745549 A EP 09745549A EP 09745549 A EP09745549 A EP 09745549A EP 2276816 A1 EP2276816 A1 EP 2276816A1
Authority
EP
European Patent Office
Prior art keywords
printing
printing ink
polycarbonate
ink
radiation
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.)
Withdrawn
Application number
EP09745549A
Other languages
German (de)
English (en)
French (fr)
Inventor
Martin Hauck
Wolfgang Schäfer
Roland KÜNZEL
Klaus Meyer
Norbert Kinzel
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.)
Marabu GmbH and Co KG
Original Assignee
Marabuwerke GmbH and Co KG
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 Marabuwerke GmbH and Co KG filed Critical Marabuwerke GmbH and Co KG
Priority to EP10016012A priority Critical patent/EP2305758B1/de
Publication of EP2276816A1 publication Critical patent/EP2276816A1/de
Withdrawn legal-status Critical Current

Links

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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/18—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. compression moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14688—Coating articles provided with a decoration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • 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
    • 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
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14688—Coating articles provided with a decoration
    • B29C2045/14704—Coating articles provided with a decoration ink decorations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate

Definitions

  • the present invention relates to a printing ink or a printing ink according to the preamble of the main claim and their use for various printing processes.
  • this ink known from the prior art is disadvantageous insofar as the solvent-containing printing inks known from the prior art tend to dry out in the sieve due to evaporation of the solvent, in particular after a certain service life without printing. This leads to the Siebverschluß and additional cleaning is necessary. In the worst case, this makes the sieve unusable.
  • Another disadvantage of this known from the prior art technology is that the drying of the ink must be done by means of hot air in the drying duct or oven; This leads to the fact that the processing is extended by the time required for drying and thus can not be optimally optimized.
  • the IR dryers used for heat drying result in increased space and energy requirements, which results in an increase in costs.
  • the need to use volatile solvents is eliminated to prevent unwanted drying in the screen during the printing process, as well as the need for solvent redensification, thereby shortening the processing time.
  • finer details can be printed and thus a higher print quality can be achieved.
  • disadvantageous washing out or deterioration of the printed image can be avoided.
  • the curing is preferably carried out under UV irradiation, LED curing or optionally with electron beam curing, with typical curing times of significantly less than 1 sec. lead to a very rapid curing of the liquid ink and / or the printing varnish.
  • the prints are printed directly without additional temperature addition by e.g. a drying channel einverarbeitbar. This significantly shortens the processing time for printing and increases productivity. It is also advantageous that by avoiding any leaching od. Like. In combination with the best adhesion to the film substrate, fine details can be printed and thus, with the screen printing process, potentially further application fields become accessible.
  • UV-curable or “radiation-curable” is also to be understood as “crosslinkable”, which means that curing of the colored film takes place by means of radical chain polymerization
  • crosslinkable means that curing of the colored film takes place by means of radical chain polymerization
  • non-radiation-curable in this context means in particular the absence of a reactive double bond.
  • Radiation-curing printing inks in addition to the binders according to the invention, such as all printing inks and / or printing varnishes, can contain many different components and, of course, have to be adapted to the respective application and the printed substrate.
  • the various components include e.g. Pigments, fillers and auxiliaries, which are usually required only in very small quantities, but are often favorable for easy processing.
  • thermoplastic, non-UV-curable polycarbonate resin in conjunction with the typically non-volatile (or at best low-volatility) monomer ensures that the ink is firmly anchored to a substrate (eg, a plastic film) and thus the finished print will be subject to stress Abrasion, heat and mechanical bending as well as the conditions as they usually arise when injecting the printed film, survives favorable. Due to the non-volatility of the individual components of the printing ink, there is no subsequent dilution or the like during processing. as an additional process step required, as is necessary for example in halogen-free solvents from the prior art.
  • polycarbonates used in the invention are highly heat-resistant and very flexible, so that they od ideally for injection molding. Like. Are suitable.
  • the printing inks or printing lacquers according to the invention are suitable for producing a laminate in such a way that a substrate printed with the printing ink according to the invention is processed on the printing side by injection molding with a (thermoplastic) plastic to form the laminate.
  • a (thermoplastic) plastic to form the laminate.
  • an object which is optimally protected against abrasion can be manufactured, in which, moreover, the typeface is optimized.
  • the reference to the basic procedure according to EP 0 691 201 B1 is given, in particular with regard to the layer structure, the substrate used and the further thermoplastic material.
  • the essential advantage of the present invention is that the ink used, for which the polycarbonate is dissolved in UV-curable monomers, permits simple radiation curability, preferably UV curability of the ink, better adhesion of the ink to the printing material Substrate, a deformability of this coated substrate without damaging the ink layer and a backfilling of such a coated substrate with thermoplastic see plastics without leaching or destruction of the ink layer can be achieved.
  • the glass transition temperature of the paint according to the invention can vary in the range from 216 ° C. (glass transition temperature of a polycarbonate binder used) to values of> 30 ° C.
  • the glass transition temperature of the polycarbonate used as binder in the color according to the invention can be both below and above the glass transition temperature of the substrate. However, it may be advantageous for the glass transition temperature of the polycarbonate used as the binder to be above the glass transition temperature of the substrate.
  • the glass transition temperature is determined according to ISO 11357.
  • the printing process can be, for example, a screen printing, rotary screen printing, pad printing, offset printing, flexographic, gravure printing or inkjet printing process.
  • the screen printing method is preferred.
  • the curing of the ink is preferably carried out with UV light in a wavelength range of 200 to 450 nm, which is sufficient to achieve a complete curing of the printing ink or the printing varnish.
  • the ink or varnish can be cured without the use of photoinitiators with electron beams.
  • UV-curable curing by way of another radiation, for example electron beams, is to be read as an alternative.
  • LED units which are almost free emit monochromatic light in the UV light range or near ultraviolet light range.
  • the curing is carried out depending on the printing task and printing machine with commercially available mercury medium-pressure lamps or doped lamps with 80-400 W / cm, preferably 120 to 200 W / cm, which are substantially focused.
  • the exposure time is coupled to the printing speed because the printing and exposure devices are coupled.
  • a usual printing speed is 1-50 impressions / min.
  • the invention preferably relates to high-temperature-resistant flexible printing inks or lacquers which
  • binders at least one polycarbonate, preferably based on geminally disubstituted dihydroxydiphenylcycloalkanes,
  • B) contain as a solvent radiation-curing monomers, preferably UV-curing monomers or monomer mixtures.
  • Suitable polycarbonates are preferably high molecular weight, thermoplastic, aromatic polycarbonates having M w (weight average molecular weight) of at least 10,000, preferably from 20,000 to 300,000, which contain bifunctional carbonate structural units of the formula (I),
  • R 1 and R 2 are independently hydrogen, halogen, preferably chlorine or bromine, Ci-C 8 alkyl, C 5 -C 6 cycloalkyl, C ⁇ -Cio-aryl, preferably phenyl, and C 7 -C 2 aralkyl preferred Phenyl-C 1 -C 4 -alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
  • R 3 and R 4 are individually selectable for each X, independently hydrogen or Ci-C alkyl, and ⁇
  • X is carbon, and n is an integer of 30 or greater, more preferably an integer of 50 to 900, most preferably an integer of 60 to 250,
  • X, R 3 and R 4 are preferably simultaneously alkyl at 1-2 atoms, in particular only at one atom.
  • Preferred alkyl is methyl; the X atoms in the alpha position relative to the diphenyl-substituted C atom (CI) are preferably not dialkyl-substituted, while the alkyl di-substitution in the beta position relative to CI is preferred.
  • the polycarbonates can be prepared according to German Patent Application P 3 832 396.6 or EP-A 0 359 953 from diphenols of the formula (Ia).
  • diphenols of the formula (Ia) may also be mixed with other diphenols, for example those of the formula (Ie)
  • thermoplastic aromatic polycarbonates
  • Suitable other diphenols of the formula (Ie) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or other cycloaliphatic radicals. may contain radicals as those of the formula (Ia) or heteroatoms as bridge members.
  • diphenols of the formula (Ie) are: hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) ether, bis (hydroxyphenyl) (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, alpha, alpha 'bis (hydroxyphenyl) diisopropylbenzenes and their ring-alkylated and ring-halogenated compounds.
  • Preferred other diphenols are, for example:
  • Particularly preferred diphenols of the formula (Ie) are, for example: 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis - (3, 5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -cyclohexane.
  • 2, 2-bis (4-hydroxyphenyl) propane is preferred.
  • the other diphenols can be used both individually and in a mixture.
  • the molar ratio of diphenols of the formula (Ia) to the other diphenols of the formula (Ie) which may be used should be between 100 mol% (Ia) to 0 mol% (Ie) and 2 mol% (Ia) to 98 mol -% (Ie), preferably between 100 mol% (Ia) to 0 mol% (Ie) and 10 mol% (Ia) to 90 mol% (Ie) and especially between 100 mol% (Ia) to 0 mol% (Ie) and 30 mol% (Ia) to 70 mol% (Ie) are.
  • the high molecular weight polycarbonates from the diphenols of the formula (Ia), optionally in combination with other diphenols, can be prepared by the known polycarbonate production processes.
  • the various diphenols can be linked together both statistically and in blocks.
  • novel polycarbonates may be branched in a manner known per se. If the branching is desired, it is possible in known manner by condensing in small amounts, preferably amounts between 0.05 and 2.0 mol% (relative to diphenols used), to three or more than three functional compounds, especially those having three or more than three phenolic hydroxyl groups.
  • Suitable branching agents having three or more than three phenolic hydroxyl groups are: phloroglucinol, 4, 6-dimethyl-2,4,8-tri- (4-hydroxyphenyl) heptene
  • Tri- (4-hydroxyphenyl) -phenylmethane 2,2-bis- [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, 2, 6-is- (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- [4- (4- hydroxyphenyl-isopropyl) -phenyl] -orthoterephthalic acid ester, tetra (4-hydroxyphenyl) -methane, tetra- [4- (4-hydroxyphenyl-isopropyl) -phenoxy] -methane and 1,4-bis- [4 ', 4' ' -dihydroxytriphenyl) -methyl] -benzene.
  • trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Suitable compounds are e.g. Phenol, tert. Butylphenols or other alkyl-substituted phenols.
  • phenols of the formula (If) are suitable
  • R is a branched Cs and / or Cg alkyl radical.
  • the chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 MoI-%, based on diphenols used.
  • the polycarbonates may preferably be prepared in a manner known per se according to the phase boundary behavior (compare H. Schnell "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, page 33ff., Interscience Publ.
  • the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase.
  • mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ie), are used.
  • chain terminators for example of the formula (If) can be added.
  • organic phase is reacted with phosgene by the method of interfacial condensation.
  • the reaction temperature is between 0 0 C and 40 0 C.
  • the optionally used branching agents can either be initially charged with the diphenols in the aqueous alkaline phase or added in the organic solvent before phosgenation.
  • diphenols of the formula (Ia) and, if appropriate, other diphenols (Ie) it is also possible to use their mono- and / or bis-chlorocarbonic acid esters, these being added dissolved in organic solvents.
  • the amount of chain terminators and of branching agents then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and optionally formula (Ie); When using chloroformates the amount of phosgene can be reduced accordingly in a known manner.
  • Suitable organic solvents for the chain terminators and optionally for the branching agents and the chloroformates are, for example, methylene chloride, chlorobenzene, in particular mixtures of methylene chloride and chlorobenzene.
  • the chain terminators and branching agents used can be dissolved in the same solvent.
  • the organic phase used for the interfacial polycondensation is, for example, methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.
  • NaOH solution serves as the aqueous alkaline phase.
  • the preparation of the polycarbonates by the interfacial process can be catalyzed in a conventional manner by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of 0.05 to 10 mol%, based on moles of diphenols used.
  • the catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.
  • the polycarbonates can be synthesized in homoge- generous phase, the so-called "pyridine process” as well as by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene.
  • the polycarbonates preferably have molecular weight M w (weight average, determined by gel chromatography after prior calibration) of at least 10,000, more preferably from 20,000 to 300,000 and in particular from 20,000 to 80,000. They may be linear or branched, they are homopolycarboxylic nate or copolycarbonates based on the diphenols of the formula (Ia).
  • the incorporation of the diphenols of the formula (Ia) has resulted in the formation of new polycarbonates with high heat resistance, which otherwise have a good property profile.
  • R 1 , R 2 and n have the meaning given for formula (I), but more preferably are hydrogen.
  • polycarbonates based on the diphenols of the formula (Ib), in which in particular R 1 and R 2 are hydrogen, furthermore have good UV stability and good flow behavior in the melt for high heat resistance, which was not to be expected, and show very good results Solubility in the monomers mentioned below.
  • the arbitrary composition with other diphenols in particular with those of the formula (Ie), can be used to vary the carbonate properties in a favorable manner.
  • Copolycarbonates are the diphenols of the formula (Ia) in amounts of 100 mol% to 2 mol%, preferably in amounts of 100 mol%.
  • % to 10 mol% and in particular in amounts of from 100 mol% to 30 mol%, based on the total amount of 100 mol% of diphenol units, contained in polycarbonates.
  • the copolycarbonate used is dissolved in one or more UV-curable monomers which are crosslinkable, for. B. due to the polymerization suitable acrylate groups or ethylenically unsaturated groups.
  • These monomers are preferably monofunctional acrylates. However, it is also possible to use di-, tri- or higher-functional acrylates or methacrylates.
  • UV-curable or radiation-curable monomers serve to dissolve the polycarbonate, but are based on a different principle compared to the solvents used and understood, for example, in EP 0 688 839 B1.
  • the solvents in the conventional sense, as used, for example, in EP 0 688 839 Bl, are used exclusively for dissolving the polycarbonate.
  • the solvents should as completely as possible, ie to almost 100%, evaporate and thus have no film-forming properties.
  • crosslinkable monomers are used which are also said to dissolve the polycarbonate, but at best they remain 100% in color, so that they are dimensionally have a pronounced influence on the properties of the cured ink and decisively influence the film properties.
  • the volatility of the radiation-curable monomers should preferably be below 5%, more preferably below 1%.
  • crosslinkable monomers isobornyl (meth) acrylate (IBO (M) A), 2-phenylethyl (meth) acrylate (PE (M) A), ethoxylated 2-phenylethoxyacrylate, methoxylated Polyethylenglykolmo- no meth) acrylates, alkoxylated tetrahydrofurfuryl (meth) acrylate, alkoxylated lauryl acrylate, alkoxylated phenyl acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isodecyl (meth) acrylate, isooctyl acrylate, octyl acrylate, tridecyl (meth) acrylate , Caprolactone acrylate, ethoxylated or alkoxylated nonylphenol (meth) acrylate, cyclic trimethylo
  • PE (M) A 2-Phenylethyl (meth) acrylate
  • EEOEA 2-(2-ethoxyethoxy) ethyl acrylate
  • MMA methyl methacrylate
  • HDDA Hexanedioldiacrylate
  • vinyl ethers can be used as crosslinkable monomers such as, but not limited to, diethylene glycol divinyl ether (DVE-2) or triethylene glycol divinyl ether (DVE-3).
  • DVE-2 diethylene glycol divinyl ether
  • DVE-3 triethylene glycol divinyl ether
  • N-vinylpyrrolidone N-vinylcaprolactam
  • N-vinylformamide NVF
  • acrylic morpholine ACMO
  • UV-curable or radiation-curable monomers are added to the binder for printing inks or lacquers.
  • These UV-curable monomers, which are also cured, may be the UV-curable monomers discussed above in connection with the copolycarbonate solution.
  • the total amount of UV-curable monomers is generally 1-99 wt.%, Preferably 25 to 85 wt.%, In particular 50 to 85 wt.%.
  • the process of crosslinking the monomers takes place, for example, via UV curing, LED curing or electron beam curing.
  • the process of radiation curing can be combined by the present invention with its described advantages with the process of in-mold technique, in particular the insert mold technique.
  • volatile organic solvents may be added in exceptional cases to optimize the printing ink or varnish for specific applications.
  • small amounts of solvents may be introduced into the paint, since a plurality 'of the active substances available on the market are dissolved in solvents or diluted by them.
  • a maximum of 10%, preferably not more than 5%, of volatile organic solvents should be used in the printing ink or printing ink. However, it is particularly preferable to dispense with the use of the volatile organic solvents.
  • the printing ink or the printing ink may contain at least one further resin in addition to the polycarbonate used.
  • the resins may be selected from a wide variety of resins. Examples include, but are not limited to: epoxy resins, polyester resins, cellulosic resins, methyl methacrylate colopolymers (eg Paraloid B-48N, Paraloid B60, Paraloid B-82 from Rohm & Haas Deutschland GmbH, In der Kroen 4, D 60489 Frankfurt, Neocryl B -810 from Neoresins Lurgiallee 6-8, D-60439 Frankfurt / Main); Ethyl methacrylate (eg Paraloid B 72 from Rohm &Haas); Butyl methacrylate copolymers (eg Degalan LP 65/12, Degalan LP 68/04 from Röhm GmbH & Co KG, Kirschenallee); liquid epoxy resins (eg Polypox E 064 from UPPC AG, Schemmerbergerstr.
  • Such additional resins may, for example, be present in an amount of from 0 to 50% by weight dry weight, based on the total mass of the paint or paint, preferably from 0 to 20% by weight, more preferably 0 to 5% by weight to some To optimize properties such as adhesion.
  • these additional passive or inert resins which are chemically distinct from the polycarbonate used as the main resin, it should be noted that they usually increase the risk of color being washed off during back molding.
  • the paints or lacquers of the invention preferably contain at least one photoinitiator, usually two and possibly three or more photoinitiators, to initiate surface and deep cure (crosslinking) of the ink with UV light.
  • the photoinitiators used should show the lowest possible tendency to yellowing, so that the color of the component is not changed and / or falsified.
  • UV-curable inks and varnishes can be selected from the usual photoinitiators used in UV-curable inks and varnishes, etc.
  • photoinitiators used in UV-curable inks and varnishes, etc.
  • 1- Hydroxycyclohexyl phenyl ketone Irgacure ® 184 from Ciba Specialty Chemicals AG, 141 Klybeckstrasse, Postfach, 4002 Basel Switzerland
  • 2-methyl-1- [4- (methylthiophenyl) -2-morpholinopropan] -1-one Irgacure ® 907 from Ciba
  • 2-hydroxy-l- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone Irgacure ® 2959 from Ciba
  • ⁇ -dimethoxy- ⁇ - phenylacetophenone Irgacure ® 651 from Ciba
  • the amount added depends largely on the choice of printing method and the type of photoinitiators used.
  • the total amount of photoinitiators is generally from 1 to 20% by weight, preferably from 2 to 10% by weight, more preferably from 3 to 7%, based on the total mass of the printing ink or the printing ink.
  • co-initiators such as amines (eg MDEA from BASF Aktiengesellschaft, Carl-Bosch-Str 38, D-67056 Ludwigshafen) or amine-modified acrylates (eg Ebecryl P115, Ecclesyl 7100 from Surface Specialties UCB, Actilane 705, Actilane 715, Actilane 755 from Akzo Nobel Resins bv., Sales Office Germany, Industriestra.
  • amines eg MDEA from BASF Aktiengesellschaft, Carl-Bosch-Str 38, D-67056 Ludwigshafen
  • amine-modified acrylates eg Ebecryl P115, Ecclesyl 7100 from Surface Specialties UCB, Actilane 705, Actilane 715, Actilane 755 from Akzo Nobel Resins bv., Sales Office Germany, Industriestra.
  • a thickener may also be present in the printing ink or lacquer according to the invention and likewise be selected from conventional materials used for this purpose in printing inks and / or printing lacquers. These include, for example, but not limited to, fumed silica, structure-modified with methacryl silane post-treated sheet silicates and castor oil derivatives and solutions of modified ureas or Polyhydroxycarboxylklareamiden.
  • the amount of thickener (s) used is usually in the range from 0 to 10% by weight, preferably 0.5 to 5% by weight and in particular 1.5 to 3% by weight, based on the total mass of the printing ink or of printing ink.
  • the printing ink or paint according to the invention also contains a defoamer and / or a leveling agent.
  • Defoamers may be selected, for example, but not limited to, from modified acrylates or modified acrylate copolymers, but also from silicone-containing compounds.
  • Leveling agents include, for example, modified polyacrylates and polysiloxanes.
  • antifoams and / or leveling agents are used in an amount of from 0.1 to 2.5% by weight, based on the total mass of the printing ink or varnish.
  • Preferred use find in the defoamers and leveling agents silicone-free products to prevent migration of these compounds and the possible delamination of the injection of the color.
  • stabilizers but not limited to, Genorad 16 from Rahn and Fluorstab UV2 from Kromachem, 10, Park Industrial Center, Tolpits Lane, Watford, Hertfordshire WD1 8SP, UK are preferably used.
  • the printing ink of the invention or the printing ink may comprise one or more fillers. These fillers are used to reduce the price and to optimize the flow properties of the printing ink and / or the printing ink.
  • fillers are not particularly critical. They may be selected from conventional fillers used in printing inks, such as, but not limited to, china clay, barium sulfate (precipitated as blanc fixe), calcium carbonate, zinc sulfide, silica, talc, aluminum silicate, aluminum hydroxide, and / or silicic acid ,
  • the amount of filler employed is generally in the range of 0 to 50% by weight, preferably 0 to 30% by weight, e.g. 20 wt.%, Based on the total mass of the ink or the paint.
  • the pigments which are preferably present in the printing ink according to the invention may be any desired pigments.
  • effect pigments such as, but not limited to, metal oxide-coated mica and metallic pigments.
  • the amount of colored pigment is usually 1 to 50% by weight, preferably 3 to 45% by weight, based on the weight of the ink, depending on the kind of the pigment, the desired hiding power and the printing method chosen.
  • White pigment is usually used in an amount of 20 to 50% by weight, preferably 25 to 45% by weight.
  • the colored pigments are i.d.R. in an amount of 1 to 20% by weight, depending on the type and color shade and the printing method used.
  • Metal oxide-coated mica and metallic pigments are used i.d.R. in an amount of 1 to 20% by weight, depending on the type and color shade and the printing method used. All pigments used must be very stable in temperature and do not decompose, sublime or change the hue due to the resulting temperature during the back molding process.
  • waxes can be added to improve the color properties.
  • Suitable waxes are commercially available. Particularly suitable are the following waxes, examples of which are commercially available products for the respective waxes; the respective source of supply is given in brackets:
  • Micro Wax DM (Finma-Chemie GmbH, Theodor-Heuss-Strasse 5, 61191 Rosbach Germany)
  • Micro Wax HTDM (Finma-Chemie GmbH, Theodor-Heuss-Strasse 5, 61191 Rosbach Germany)
  • Deurex MA 7020 (Deurex Micro-Technologies GmbH, Dr. Bergius Strasse 18/20; 06729 Tröglitz Germany)
  • Printwax MXF 9510 D (Deurex Micro-Technologies GmbH, Bergius Strasse 18/20, 06729 Tröglitz Germany)
  • Printwax MX. 9815 D (Deurex Micro-Technologies GmbH, Bergius Strasse 18/20, 06729 Tröglitz Germany)
  • the concentration of the wax is preferably 0% by weight to 10% by weight, more preferably 0% by weight to 3.0% by weight and particularly preferably 0-2% by weight, based on the weight of the printing ink or of the printing ink.
  • an adhesion promoter in an amount of from 0.01 to 20% by weight, preferably from 1 to 10% by weight, based on the weight of the ink or the varnish, can be added to the printing ink or varnish for printing.
  • These can be isocyanate adhesion promoters, for example aliphatic polyisocyanates, such as hexamethylene diisocyanate (HDI), trimethylhexane diisocyanate (TMHDI), cycloaliphatic polyisocyanates, such as isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate (HXDI) or diisocyanatodicyclohexylmethane (HMDI), and aromatic polyisocyanates, such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) or diisocyanatodiphenylmethane (MD
  • silane coupling agents such as alkylsilanes, vinylsilanes, methacryloxysilanes, epoxysilanes, aminosilanes, urea-silanes, chlorosilanes and isocyanatosilanes, and aminosilanes, such as, for example, Aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, bis (gamma-trimethoxysilylpropyl) -amine, N-phenyl-gamma-aminopropyltrimethoxysilane and N-jbeta- (
  • Preferred printing processes are screen printing, rotary screen printing, digital printing, flexographic printing, book printing, offset printing and gravure printing. Particularly preferred is the screen printing.
  • Common substrates printed with the printing ink or varnish and used in the in-mold process include polycarbonate, pretreated polyester, ABS, PMMA, polycarbonate / polyester blends, polycarbonate / ABS blends, without themselves to limit it. These films are offered by Bayer Material Science (Bayfol®, Makrolon®, Makrofol®, Bayblend®), GE. Structured Products (Lexan®) and Autotypes (Autoflex Hiform TM, Autoflex Xtra-Form TM).
  • the substrates used are preferably films of polycarbonates or polycarbonates / polyester blends.
  • the common sprayed materials which can be used to back coat the printing ink or varnish applied to the film are particularly, but not exclusively, polyesters, polycarbonates, polystyrene, ABS and PMMA.
  • Preferred material for back molding is polycarbonate or various polycarbonate blends.
  • Exemplary polycarbonates of the formula (I-h) were prepared as follows:
  • the glass transition temperature of the polymer was determined to be 157 ° C. (DSC).
  • polycarbonate 1 As for polycarbonate 1, a mixture of 181.4 g (0.79 mol) of bisphenol A and 63.7 g (0.21 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane converted to polycarbonate. The polycarbonate showed a relative solution viscosity of 1.263.
  • the glass transition temperature of the polymer was determined to be 167 ° C. (DSC).
  • polycarbonate 1 a mixture of 149.0 g (0.65 mole) of bisphenol A and 107.9 g (0.35 mole) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.263.
  • the glass transition temperature of the polymer was determined to be 183 ° C. (DSC).
  • the polycarbonate showed a relative solution viscosity of 1.251.
  • the glass transition temperature of the polymer was determined to be 204 ° C. (DSC).
  • polycarbonate 1 a mixture of 44.2 g (0.19 mol) of bisphenol A and 250.4 g (0.81 mol) of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane converted to polycarbonate.
  • the polycarbonate showed a relative solution viscosity of 1.248.
  • the glass transition temperature of the polymer was determined to be 216 ° C (DSC).
  • the glass transition temperatures were determined by DSC (Differential Scanning Calorimetry) according to ISO 11357. To determine the glass transition temperatures, the samples were previously dried in a vacuum oven for 24 hours
  • screen printing inks were prepared as follows:
  • UV-curable monomer 4- (1-oxo-2-propenyl) morpholine 20% by weight of the binder from Bayer Material Science (polycarbonate 4, see above) was dissolved in 80% by weight of UV-curable monomer 4- (1-oxo-2-propenyl) morpholine.
  • UV-curable monomer 4- (1-oxo-2-propenyl) morpholine further monofunctional acrylates, a diacrylate, photoinitiators, leveling agents, thickener and pigment were added, predispersed with a dissolver and with the aid of a three-roll mill or a Perlmühle a color produced with a particle size of ⁇ lO ⁇ m.
  • the invention is described by the examples 1 and 2 listed in Tab. 1 and 2, without being limited thereto.
  • Example 1 (Inventive): Blue color for screen printing
  • Example 2 (according to the invention): white ink for screen printing
  • the glass transition temperature of the color according to the invention from Example 1 was determined at 156 ° C. and from Example 2 at 88 ° C. (DSC).
  • the screen printing inks of Examples 1 and 2 having a viscosity of approximately 4,000 mPa * s were each screen printed 150-31 printed on a polycarbonate film (Makrofol ® DE-4; 375 ⁇ m; Bayer material Science AG) and at a speed of 15m / min using 2 x 120 cured W / cm high pressure mercury vapor lamps.
  • Example 3 blue ink for screen printing
  • the binder dissolved in UV-curable monomer 4- (1-oxo-2-propenyl) morpholine was a diacrylate, photoinitiators, Leveling agent, thickener and pigment added, predispersed with a dissolver and prepared using a three-roll mill or a bead mill, a color with a particle size of ⁇ lO ⁇ m.
  • the glass transition temperature of the paint according to the invention from Example 3 was determined at 160 ° C. (DSC).
  • the screen printing ink of the invention For coating a film with the screen printing ink of the invention, the screen printing ink with a viscosity of about 4,000 mPa * s (cone-plate system at a shear rate of
  • coated films (laminates) prepared according to Examples 1 to 7 were described as follows Deformability tested.
  • the deformation experiments were carried out on a SAMK 360 high-pressure forming machine (HPF-deformation machine) Bj. 2000 by Niebling. For the evaluation of the deformation properties, the experiments have been carried out with a heating-ventilation blending tool.
  • the dimensions of the component were about 190 xl20 mm with different openings to evaluate the drawing here.
  • the mold temperature was 100 ° C. Before deformation, the films were preheated in a heating zone. The heating time was 16 seconds in all experiments, which gave a film temperature of about 150-160 0 C. For the evaluation in each case 5 films from the respective examples were deformed in succession. The evaluation was carried out visually and the results are summarized in Tab. 7.
  • coated films produced according to Examples 1 to 7 and shaped according to Example 8 were tested for their injectability as described below.
  • FIM Film Insert Molding
  • the experiments were carried out on an injection molding machine from Arburg.
  • the Arburg Allrounder 570 C has a clamping force of max. 200 to and is year 2003.
  • the different films were back-injected with PC / ABS at 260 0 C.
  • the filling time was 2 seconds and the injection pressure was measured at 1000 bar.
  • the tool temperature has been set to 60 0 C by default.
  • the tool has a hot runner nozzle which uses a cold distributor to guide the plastic into the mold cavity via auxiliary pins. This results in high temperatures and shear, which can wash out the printed ink in case of excessive stress.
  • the moldings from example 9 were exposed to a climate storage. Here were the exams in one

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KR101675600B1 (ko) 2016-11-11
US20110118377A1 (en) 2011-05-19
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