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WO1991000312A1 - Systeme liant durcissable sous l'effet de rayonnements contenant des composes sulfonyles alpha-substitues comme photo-activateurs - Google Patents

Systeme liant durcissable sous l'effet de rayonnements contenant des composes sulfonyles alpha-substitues comme photo-activateurs Download PDF

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Publication number
WO1991000312A1
WO1991000312A1 PCT/EP1990/000927 EP9000927W WO9100312A1 WO 1991000312 A1 WO1991000312 A1 WO 1991000312A1 EP 9000927 W EP9000927 W EP 9000927W WO 9100312 A1 WO9100312 A1 WO 9100312A1
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WO
WIPO (PCT)
Prior art keywords
radiation
formula
compounds
acid
free
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.)
Ceased
Application number
PCT/EP1990/000927
Other languages
German (de)
English (en)
Inventor
Ekkehard Bartmann
Jörg OHNGEMACH
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.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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 Merck Patent GmbH filed Critical Merck Patent GmbH
Priority to FI910951A priority Critical patent/FI910951A0/fi
Priority to BR909006841A priority patent/BR9006841A/pt
Priority to KR1019910700219A priority patent/KR920701331A/ko
Publication of WO1991000312A1 publication Critical patent/WO1991000312A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the invention relates to radiation-curable binder systems which contain certain ⁇ -substituted sulfonyl compounds as photoactivators. These are binder systems based on free-radically and / or acid-curable components in which the photoactivators according to the invention function as free-radical-forming photoinitiators and / or as radiation-activatable latent acid catalysts.
  • a large part of the binder systems in paint and coating technology is based on heat-curing materials, in which cross-linking and curing takes place through polycondensation.
  • Base materials capable of polycondensation are usually aminoplast synthetic resins, the thermal curing of which is catalyzed by acids, in particular organic sulfonic acids.
  • a typical and very frequently used acid catalyst is p-toluenesulfonic acid (PTS).
  • PTS p-toluenesulfonic acid
  • acid-curable systems have the disadvantage that, if they are mixed with the acid catalyst, they have only a limited shelf life and soon gel if they are not processed within a shorter time.
  • Sulfonic acid catalysts in "blocked" form for example as amino salts or oxime esters of hydroxamic acids, enable a better one
  • photochemically induced curing has also become very important in coating and coating technology, with special radiation-curable compositions being used which contain photoactivators or photoinitiators for converting the radiation energy.
  • Radiation curing is characterized in particular by high speed and low energy consumption.
  • the most important photopolymerization reaction for practical use is the radical polyaddition of ethylenic double bonds.
  • Corresponding radiation-curable systems are therefore based on materials which contain free-radically polymerizable or crosslinkable ethylenic double bonds and free-radical-forming photoinitiators.
  • the compounds known from EP 192 967 have the disadvantage that they are only moderately reactive. For a defined curing result, comparatively high radiation outputs and / or long irradiation times are required. In addition, these compounds have the disadvantage that their synthesis is relatively complex and is linked to the use of starting materials and solvents which are not harmless and the formation of harmful by-products. Their industrial production and use from an economic point of view and including today's environmental and occupational safety issues is therefore problematic.
  • the aim of the invention was therefore to find further compounds which can be used as free-radical-forming photoinitiators and as radiation-activatable latent acid catalysts in radiation-curable binder systems based on free-radically and / or acid-curable components.
  • the sought compounds should have a higher reactivity than conventionally used compounds and should be as simple and easy to access as possible.
  • EP 192 967 superior to known sulfonylacetophenone compounds.
  • the invention thus relates to the use of compounds of the formula I as free-radical-forming photoinitiators and / or radiation-activatable latent acid catalysts in binder systems based on free-radically and / or acid-curable components.
  • the invention furthermore relates to radiation-curable binder systems based on free-radically and / or acid-curable components which contain an effective amount of at least one compound of the formula I as free-radical-forming photoinitiators and / or as radiation-activatable latent acid catalysts.
  • the invention furthermore relates to a process for curing binder systems based on free-radically and / or acid-curable components, an effective amount of at least one compound of the formula I being added to them and curing by irradiation with UV light of a wavelength between 200 and 450 nm or by combined irradiation and heating.
  • the invention relates to a method for producing a radiation-hardened coating on a substrate, this being done with a binder telsystem based on radical and / or acid-curable components, containing an effective amount of at least one compound of formula I, coated and the curing by irradiation with UV light of a wavelength between 200 and 450 nm or by combined irradiation and heating.
  • the ⁇ -substituted sulfonyl derivatives of the formula I with the meanings given above are essentially compounds known per se.
  • the substituent X in the ⁇ -position to the sulfonyl group can be a hydroxyl or an amino group, which in turn can itself be substituted. Accordingly, the substructures of sub-formulas Ia, Ib and Ic result with the meanings given above.
  • Ia to Id are about the following:
  • the compounds benzoyl- (p-tolyl-sulfonyl) -methanol, (m-nitro-benzoyl) - (phenyl-sulfonyl) -methanol and benzoyl- (p-methoxy-phenyl-sulfo) are particularly preferred nyl) methanol, especially the compound benzoyl- (p-tolyl-sulfonyl) -methanol.
  • the compounds of the formula I can be used very advantageously as radiation activators for curing binder systems. Their particular advantage is that radicals can be liberated from them by the action of radiation and that they can be broken down into radiation-induced acidic cleavage products, which then act as acid catalysts. This acid degradation is also thermally inducible, so that additional promotion or sole triggering of this
  • the compounds of the formula I can be used equally as free-radical-forming photoinitiators in binder systems based on free-radically curable components and as radiation-activatable latent acid catalysts in binder systems based on acid-curable components and in mixed systems, so-called hybrid binder systems, which contain free-radical components and acid-curing components.
  • the compounds of the formula I are used according to the invention as photoactivators in such binder systems by simple mixing with these binder compositions, if appropriate with gentle heating or the addition of minor amounts of solvent to promote homogeneous distribution.
  • the compounds of the formula I are sufficiently effective for common applications and processing processes if they are present in the binder systems in a proportion of 0.1 to 20% by weight. Their proportion is preferably between 1 and 10% by weight; Their use in a proportion of about 2% by weight, based on the total amount of the binder system, is particularly expedient and economical.
  • the photochemical activation of the compounds of the formula I can be carried out by simple mixing with these binder compositions, if appropriate with gentle heating or the addition of minor amounts of solvent to promote homogeneous distribution.
  • the compounds of the formula I are sufficiently effective for common applications and processing processes if they are present in the binder systems in a proportion of 0.1 to 20% by weight. Their proportion is preferably between 1 and 10% by weight; Their use in a proportion of about 2% by weight, based on the
  • Radiation-curable binder systems based on free-radically and / or acid-curable components, in which the compounds of the formula I can be used according to the invention as free-radical-forming photoinitiators and / or radiation-activatable latent acid catalysts, are known per se.
  • free-radically curable components is usually understood to be a mixture which contains at least one ethylenically unsaturated compound which can be photopolymerized by free radicals and, if appropriate, further customary additives. Practically all materials which have olefinically unsaturated double bonds are suitable as free-radically polymerizable components. These can in particular be monomers, oligomers and polymers, each with at least one or expediently with several unsaturated functions of the acrylate or vinyl type. Corresponding materials are known to the expert in great abundance.
  • acrylic compounds examples include acrylic compounds, in particular acrylates of aliphatic and aromatic mono- or polyhydroxy compounds, such as (meth) acrylic acid including theirs Salts and amides, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, hydroxyethyl (meth) acrylate, vinyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol propane di (meth) acrylate, pentaerythritol tri ( meth) acrylate, further vinyl compounds such as vinyl chloride, vinylidene chloride, styrene, divinylbenzene, N-vinylpyrrolidone, N-vinylcarbazole.
  • acrylic acid including theirs Salts and amides
  • acrylic acid alkyl esters examples include hydroxyethyl (meth) acrylate, vinyl (meth) acrylate, ethylene
  • higher molecular and polymeric binder components are, for example, acrylated polyester, acrylate, epoxy, urethane, polyamide and silicone resins.
  • Radiation-curable binder systems are predominantly mixtures of several of the listed low molecular weight and high molecular weight unsaturated components.
  • Acid-curable binder systems which likewise represent the area of use of the compounds of the formula I according to the invention, are all those systems which contain at least one acid-catalyzed component capable of polycondensation.
  • These are mainly synthetic resin materials based on melamine or urea, which can also be modified in a variety of ways. These materials are familiar to the person skilled in the art; They are manufactured in large quantities and modified for their various properties in their material properties industrially.
  • a typical example of a melamine base material is hexamethoxymethylmelamine.
  • the acid-curable binder systems can contain any further components in different proportions, as are customary in the technology of aminoplast plastics, for example alkyd, phenol, polyester, acrylic and polyvinyl resins or mixtures thereof.
  • the compounds of the formula I are suitable as radiation-activatable curing catalysts, in particular also for hybrid binder systems which are acid-catalyzed, polycondensation-capable and free-radically polymerizable parts included. According to the invention, they can be activated purely photochemically and expediently combined photochemically and thermally, whereby they act equally as radical and acid generators and thus effect the curing of the different hybrid system components practically simultaneously.
  • Acid-curable components for such hybrid systems are all materials mentioned above, that is to say materials which can be crosslinked thermally, for example by polycondensation or polyaddition, but not by free radicals. Examples include acid-curable melamine resins and reactive resins that form polyurethane or polyester.
  • the proportion of acid-curable and free-radically polymerizable components can be varied within wide ranges, for example between 10 and 90% by weight.
  • the radiation-curable binder systems can also be in the form of aqueous dispersions, the water content of which is normally removed by brief heating after coating.
  • binder systems which can be hardened with the compounds of formula I as photoactivators, whether on the basis of purely free-radically polymerizable, purely acid-hardenable or hybrid-based, can be varied widely in their qualitative and quantitative compositions, and in particular they can also contain further constituents and additives.
  • the proportion of reactive components should expediently not fall below 10% by weight.
  • the application extends primarily to the production of thin layers such as lacquer coatings on all the usual materials and substrates. These can primarily be paper, wood, textile supports, plastic and metal. An important area of application is also the drying or hardening of printing inks and screen printing materials, the latter of which are preferably used in the surface coating or design of, for example, cans, tubes and metal caps.
  • the binder systems according to the invention containing compounds of the formula I or the coatings produced therewith can be cured by the action of radiation energy, in particular from the UV wavelength range between 200 and 450 nm.
  • radiation energy in particular from the UV wavelength range between 200 and 450 nm.
  • the usual high-pressure mercury vapor, medium-pressure or low-pressure lamps as well as xenon and tungsten lamps can be used as beam sources.
  • thermosetting systems To promote thermal energy.
  • the additional thermal activation takes place in the temperature range customary for acid-catalyzed thermosetting systems. This is approximately between 80 and 150 ° C, preferably between 100 and 120 ° C.
  • a particularly favorable property of the compounds of the formula I here is that their photochemical and thermal activity can be varied and matched to one another by selective choice of the substituents and the respective sensitivity can be specifically controlled.
  • the hardening can take place discontinuously as well as continuously.
  • the irradiation time depends on the type of implementation, on the type and amount of the polymerizable materials used, on the type and concentration of the photoactivators used and on the intensity of the light source.
  • Coatings it is usually in the range of a few seconds to minutes. Depending on the temperature and the binder system, the duration of any additional heat treatment, which may be expedient, until complete hardening is in the range from minutes to a few hours.
  • the compounds of formula I have comparable radiation activators, in particular those from
  • EP 192 967 known ⁇ -sulfonylacetophenones, the special, not expected advantage that they lead to significantly higher layer hardness under comparable application and processing conditions. Shorter irradiation times are required to achieve certain predetermined layer hardnesses. Furthermore, they are considerably superior to the known radiation-activatable and thermal acid catalysts with regard to the storage stability of the binder systems which have been mixed with them. They also show no tendency to adversely affect the hardened end product, in particular to yellow.
  • the ready-to-use paint samples were then applied to glass plates (10 cm ⁇ 10 cm) in a layer thickness of 80 ⁇ m and flashed off at room temperature for 10 minutes to remove the solvent.
  • the coated glass plates were in a UV laboratory dryer (type BE 22 from Beltron) at belt speeds of 2.5 m / min to 40 m / min (exposure times from 1.5 s / m to 24 s / m) passed at a distance of about 10 cm under a medium pressure mercury lamp with an output of 80 W / cm. After the UV radiation, the coated plates were cured in a laboratory drying cabinet at 120 ° C. for 30 minutes. After hardening and cooling, the condition of the surface was determined by sensors and about 20 hours after baking, the pendulum hardness according to König (DIN 53 157) was determined as a measure of the hardening result.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Des systèmes liants à base de composants durcissables par des radicaux et/ou des acides contiennent certains composés alpha-substitués en tant que photo-initiateurs formateurs de radicaux et/ou en tant que catalyseurs d'acides latents susceptibles d'être activés sous l'effet de rayonnements.
PCT/EP1990/000927 1989-06-30 1990-06-13 Systeme liant durcissable sous l'effet de rayonnements contenant des composes sulfonyles alpha-substitues comme photo-activateurs Ceased WO1991000312A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
FI910951A FI910951A0 (fi) 1989-06-30 1990-06-13 Straolningshaerdbara bindemedelssystem med a-substituerade sulfonylfoereningar som fotoaktivatorer.
BR909006841A BR9006841A (pt) 1989-06-30 1990-06-13 Sistemas aglutinantes curaveis por radiacao contendo compostos de sulfonila-substituidos como fotoativadores
KR1019910700219A KR920701331A (ko) 1989-06-30 1990-06-13 광활성제로서 α-치환된 술포닐 화합물을 함유하는 방사-경화 결합제 계

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3921459A DE3921459A1 (de) 1989-06-30 1989-06-30 Strahlungshaertbare bindemittelsysteme mit (alpha)-substituierten sulfonylverbindungen als fotoaktivatoren
DEP3921459.1 1989-06-30

Publications (1)

Publication Number Publication Date
WO1991000312A1 true WO1991000312A1 (fr) 1991-01-10

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Application Number Title Priority Date Filing Date
PCT/EP1990/000927 Ceased WO1991000312A1 (fr) 1989-06-30 1990-06-13 Systeme liant durcissable sous l'effet de rayonnements contenant des composes sulfonyles alpha-substitues comme photo-activateurs

Country Status (10)

Country Link
EP (1) EP0431122A1 (fr)
JP (1) JPH04500698A (fr)
KR (1) KR920701331A (fr)
AU (1) AU5928290A (fr)
BR (1) BR9006841A (fr)
CA (1) CA2035460A1 (fr)
DD (1) DD296301A5 (fr)
DE (1) DE3921459A1 (fr)
WO (1) WO1991000312A1 (fr)
ZA (1) ZA905121B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2662141B2 (ja) * 1991-05-20 1997-10-08 エイ・ティ・アンド・ティ・コーポレーション デバイスの製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4395520A (en) * 1982-01-20 1983-07-26 Union Carbide Corporation Process for curing thermosetting resins using sulfur dioxide containing compounds as latent catalysts
EP0084515A2 (fr) * 1982-01-11 1983-07-27 Ciba-Geigy Ag Composition durcissable par un acide contenant un catalyseur masqué et procédé de durcissement
US4477618A (en) * 1982-09-29 1984-10-16 Ppg Industries, Inc. Aminoplast curable coating compositions containing sulfonic acid esters as latent acid catalysts
EP0192967A1 (fr) * 1985-01-28 1986-09-03 FRATELLI LAMBERTI S.p.A. Dérivés sulfurés de cétones aromatiques-aliphatiques et aliphatiques comme initiateurs de photo-polymérisation
EP0306472A2 (fr) * 1987-09-03 1989-03-08 Monsanto Company Composition de résine durcies avec des catalyseurs à base d'acide bloqué
EP0306471A2 (fr) * 1987-09-03 1989-03-08 Monsanto Company Catalyseurs à base d'acide bloqué

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0084515A2 (fr) * 1982-01-11 1983-07-27 Ciba-Geigy Ag Composition durcissable par un acide contenant un catalyseur masqué et procédé de durcissement
US4395520A (en) * 1982-01-20 1983-07-26 Union Carbide Corporation Process for curing thermosetting resins using sulfur dioxide containing compounds as latent catalysts
US4477618A (en) * 1982-09-29 1984-10-16 Ppg Industries, Inc. Aminoplast curable coating compositions containing sulfonic acid esters as latent acid catalysts
EP0192967A1 (fr) * 1985-01-28 1986-09-03 FRATELLI LAMBERTI S.p.A. Dérivés sulfurés de cétones aromatiques-aliphatiques et aliphatiques comme initiateurs de photo-polymérisation
EP0306472A2 (fr) * 1987-09-03 1989-03-08 Monsanto Company Composition de résine durcies avec des catalyseurs à base d'acide bloqué
EP0306471A2 (fr) * 1987-09-03 1989-03-08 Monsanto Company Catalyseurs à base d'acide bloqué

Also Published As

Publication number Publication date
KR920701331A (ko) 1992-08-11
AU5928290A (en) 1991-01-17
DE3921459A1 (de) 1991-01-03
DD296301A5 (de) 1991-11-28
JPH04500698A (ja) 1992-02-06
CA2035460A1 (fr) 1990-12-31
BR9006841A (pt) 1991-08-06
EP0431122A1 (fr) 1991-06-12
ZA905121B (en) 1991-05-29

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