WO2001027207A1 - Procede de fabrication de revetements par durcissage uv - Google Patents

Procede de fabrication de revetements par durcissage uv Download PDF

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Publication number
WO2001027207A1
WO2001027207A1 PCT/EP2000/010060 EP0010060W WO0127207A1 WO 2001027207 A1 WO2001027207 A1 WO 2001027207A1 EP 0010060 W EP0010060 W EP 0010060W WO 0127207 A1 WO0127207 A1 WO 0127207A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
structural units
weight
curing
amount
Prior art date
Application number
PCT/EP2000/010060
Other languages
German (de)
English (en)
Inventor
Antje Meier
Wolfgang Kranig
Erich Beck
Wolfgang Reich
Wolfgang Paulus
Wolfgang Schrof
Original Assignee
Basf Aktiengesellschaft
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 Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU10245/01A priority Critical patent/AU1024501A/en
Publication of WO2001027207A1 publication Critical patent/WO2001027207A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate

Definitions

  • the invention relates to the production of tack-free coatings by UV curing thin photoinitiator-poor or photoinitiator-free coating compositions which contain acrylate and / or methacrylate esters and an ether component.
  • UV rays when curing unsaturated coating compositions, it is usually preferable to harden them with UV rays. While the presence of photoinitiators is not necessary for the curing of coating compositions with electron beams, photoinitiators which absorb the UV radiation, form radicals or protons and photopolymerization or photocrosslinking are added to the mixtures for curing the photosensitive mixtures start.
  • the amount of photoinitiators added is more than 1% by weight of the hardenable unsaturated compounds, generally even more than 3% by weight, the more precise amount required, inter alia, depending on the type of application of the UV-hardenable mixtures. UV curing under an inert gas atmosphere allows a certain reduction in the amount of photoinitiator required.
  • a photocurable coating composition containing a photoimtiator is often more unstable than a corresponding composition without a photoimtiator. Since photoinitiators are among the expensive components of a UV-hardenable coating material, UV-hardenable coating materials that contain no photoinitiators or only a small amount of them are advantageous. Also, photoinitiators or their fragments resulting from the irradiation with UV light often lead to yellowing or even odor pollution of the coating materials used. Finally, in some cases, the coating compositions may contain photoinitiators or their decomposition processes that occur during curing. products lead to toxic concerns when used.
  • EP-A 618 237 describes curing without photoinitiators by means of photochemically initiating donor-acceptor complex-forming monomers which polymerize after UV exposure.
  • a disadvantage is the sensitivity to hydrolysis of the vinyl compounds used, which can easily lead to odor-intensive acetaldehyde.
  • Resin mixtures, in particular with additives, pigments and other additives which have an acidic character, are generally not stable in storage.
  • the invention thus relates to a process for the production of tack-free, low-migration coatings by UV curing of a coating composition containing at least one olefinically unsaturated compound, optionally a photoinitiator and possibly conventional additives, which is characterized in that the coating composition contains
  • the structural units (A) and (B) can be contained in different compounds and / or together in at least one compound of the coating composition, and the curing of the coating composition with UV rays in the presence of less than 0.1% by weight of a Photoinitiators or in the absence of a photoinitiator, the percentages each refer to the total amount of UV-hardenable olefinically unsaturated compounds contained in the coating composition.
  • the structural units (A) and (B) are preferably contained together in at least one hardenable acrylate and / or methacrylate compound, preferably in an acrylic ester compound.
  • Compounds of this type which contain both acrylic ester and / or methacrylic ester groups and> CH-0-Structural units as aliphatic ether components are, for example, commercially available (meth) acrylic acid esters of ethoxylated and / or propoxylated polyalcohols and methacrylic acid esters and preferably acrylic acid esters of hydroxyl group-containing polyethers, such as those obtained by adding ethylene oxide and / or propylene oxide or mixtures thereof to aliphatic hydroxyl compounds can.
  • Examples of compounds with structural units (A) and (B) in the same compound are, for example, ether (meth) acrylates such as tripropylene glycol di (meth) acrylate, but preferably methacrylates and in particular acrylates, which are obtained by alkoxylation, in particular ethoxylation and / or propoxylation, of polyalcohols , preferably from those having 2 to 8 carbon atoms and 2 to 6 hydroxyl groups, and subsequent esterification or partial esterification with methacrylic acid or, in particular, acrylic acid to give poly (meth) acrylates.
  • ether (meth) acrylates such as tripropylene glycol di (meth) acrylate, but preferably methacrylates and in particular acrylates, which are obtained by alkoxylation, in particular ethoxylation and / or propoxylation, of polyalcohols , preferably from those having 2 to 8 carbon atoms and 2 to 6 hydroxyl groups, and subsequent esterification or partial esterification
  • polyalcohols with 2 to 6 hydroxyl groups examples include pentaerythritol, dipentaerythritol, trimethylolpropane, ditrimethylolpropane, sorbitol, glycerol, ethylene glycol, propylene glycol, hexanediol, neopentyl glycol and the like.
  • Very suitable polyalcohols or polyalcohol mixtures are those which contain more than 2, in particular at least 3.5 and particularly preferably at least 4, hydroxyl groups.
  • the then alkoxylated polyalcohols in particular contain on average 1 to 5 alkoxy groups and preferably 1 to 3 alkoxy groups per hydroxyl group of the polyalcohol, ethoxy and propoxy groups being preferred as alkoxy groups.
  • the alkoxylated polyalcohols are then reacted in a manner known per se with methacrylic acid, acrylic acid or mixtures thereof, preferably with acrylic acid, to give the corresponding esters or partial esters.
  • Suitable further compounds used according to the invention with the structural units (A) and (B) in the same unsaturated compound are polyether (meth) acrylates, polyester (meth) acrylates modified with ether groups and epoxyacrylates modified in such a way as they are e.g. in P. Oldring, Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, J.Wiley and Sons, New York, and Sita Technology Ltd., London, 1991, especially in
  • volume II (prepolymers and reactive diluents) are described. Of these, the compounds described are relevant, which contain the structural units in the amounts mentioned.
  • the (meth) acrylate and> CH-0 ether structural units need not be bound in the same chemical molecule in the amounts indicated, but can also be present in different compounds. It is thus possible for the coating compositions to contain (meth) acrylates, to which ether compounds having the> CH-0 ether structural units have been mixed in the stated amounts.
  • (meth) acrylate compounds with in particular 2 and preferably at least 3.5 (meth) acrylate structural units in the molecule can be admixed with compounds which have the> CH-0 structural units in the required amount Contain amount, such as block copolymers of propylene oxide and ethylene oxide or other polyether compounds such as polyether acrylates with a sufficient proportion of> CH-0 ether structure elements.
  • Photoinitiators for the coating compositions of the inventive method are used in amounts of less than 0.1% by weight, i.e. 0 to 0.099% by weight, added, in particular in an amount of less than 0.01% by weight, the percentages relating to the total amount of the olefin-unsaturated compounds which can be hardened with UV rays and are contained in the coating composition. It is particularly advantageous to harden the coating compositions in the absence of photoinitiators with UV rays.
  • Suitable photoinitiators are the known photoinitiators, in particular those of the benzophenone, thioxanthone, ⁇ -hydroxyketone, ⁇ -dicarbonyl compound, acylphosphmoxide, bis-acylphosph oxide and acylphosphate sulfide type.
  • photoinitiators examples include benzophenone, hydroxycyclohexylphenyl ketone, 4-methylbenzophenone, 2, 4-dimethylbenzophenone, 2-chlorobenzophenone, 4-methoxybenzophenone, anthrachmon, 2-ethylanthrachmon, thioxanthone, 1- and 2-isopropylthiooxanthone -D ⁇ methylbenzoyld ⁇ phenylphos- phmoxid.
  • photoinitiators for Free Radical, Catiomc, Anionic Polymerization
  • 2nd edition from the series of P.Oldrmg, "Chemistry and Technology of UV & EB Formulation for Coatmgs, Inks.” & Paints “, J. Wiley and Sons, New York and Sita Technology Ltd., London.
  • UV lamps which emit radiation components of less than 300 nm, such as excimer lamps, pulsed emitters, lasers and high-pressure mercury lamps, are preferred as UV light sources for UV curing in accordance with the method according to the invention, preference being given to high-pressure mercury lamps are.
  • the UV curing of the coating compositions can be carried out in the presence of air, but is preferably carried out under an inert gas atmosphere such as under nitrogen, with generally higher reactivity being achieved and it being possible to cure faster.
  • the coating compositions used according to the invention can contain additives in customary amounts, such as leveling agents, defoamers, matting agents, pigments, dispersing agents, solvents or water, but also additional binders and reactive thinners. Coating compositions with a solids content of 100% by weight are preferred. If the coating compositions contain solvents and / or water, it is advisable to dry them before the UV radiation at relatively low temperatures, for example at 50 to 80 ° C. for 15 to 50 minutes. The coating compositions can be applied to the substrates using customary coating methods, such as by rolling, knife coating, spraying, pouring, dipping, etc., to match the desired layer thickness.
  • the suitable layer thickness for clear lacquer layers is 5 - 15 ⁇ m, in general the layer thickness naturally depends on the components and the application of the coating material.
  • the suitable hardenable layer thickness can easily be determined by a few preliminary tests.
  • the layer thickness for curing clearcoats should not exceed 15 ⁇ m in the practical absence of photoinitiators.
  • Coating compositions used according to the invention are particularly suitable for lacquers, printing inks, photoresists and printing plates.
  • the coatings according to the invention are particularly suitable for the production of film top coats.
  • the tape speed (m / min) during UV curing was determined as a measure of the reactivity, with which a liquid lacquer film of 8 ⁇ m thickness, applied with a box squeegee on white paper, under an undoped high-pressure mercury lamp ( Power 120 W / cm lamp length, lamp distance to the substrate 12 cm) can be passed through in order to obtain a scratch-resistant and adhesive coating against the fingernail.
  • Monomeric PEA PEA PEA PEA (parts) 100 100 100 100 100 100 100 100 100 100
  • UV curing was carried out using a high-pressure mercury lamp (power 120 W / cm, lamp distance from the substrate 12 cm) at a belt speed of 10 m / mm (total UV dose 640 mJ / cm 2 ) in air and under nitrogen.
  • the degrees of hardness of the resulting approximately 100 ⁇ m thick films were assessed using pendulum vapor measurements according to Konig (according to DIN 53157). The results are shown in Table 4, in which Example 13 represents a comparative test (W).
  • PI 1 hydroxycyclohexylphenyl ketone
  • PI 2 benzophenone

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de fabrication de revêtements non-adhérents, à migration et jaunissement réduits, en particulier de fabrication de couches de recouvrement de feuilles. Selon ce procédé, les masses de revêtement peuvent être durcies avec moins de 0,1 % en poids d'un photoinitiateur, voire sans photoinitiateur, au moyen de rayons UV, lorsque les masses de revêtement contiennent certaines quantités minimales de groupes (méth)acrylate (A), et d'unités de structure >CH-O-éther (B), (A) et (B) pouvant être contenus ensemble dans une molécule ou dans des molécules différentes. Du fait de la réduction de la quantité de photoinitiateur, ou de la suppression du photoinitiateur, ledit procédé présente de nombreux avantages économiques, applicatifs, et toxicologiques.
PCT/EP2000/010060 1999-10-13 2000-10-12 Procede de fabrication de revetements par durcissage uv WO2001027207A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10245/01A AU1024501A (en) 1999-10-13 2000-10-12 Method for the production of coatings by uv-hardening

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19949383A DE19949383A1 (de) 1999-10-13 1999-10-13 Verfahren zur Herstellung von Beschichtungen durch UV-Härtung
DE19949383.9 1999-10-13

Publications (1)

Publication Number Publication Date
WO2001027207A1 true WO2001027207A1 (fr) 2001-04-19

Family

ID=7925509

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2000/010060 WO2001027207A1 (fr) 1999-10-13 2000-10-12 Procede de fabrication de revetements par durcissage uv

Country Status (3)

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AU (1) AU1024501A (fr)
DE (1) DE19949383A1 (fr)
WO (1) WO2001027207A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022043180A1 (fr) 2020-08-28 2022-03-03 Basf Se Procédé de séchage uv de dispersions de peinture de polyuréthane à base d'eau sans initiateurs de surface pouvant être activés par uv-c

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6900252B2 (en) 2001-05-16 2005-05-31 Alcatel UV-curable acrylate coatings for food packaging
ATE319112T1 (de) * 2001-12-06 2006-03-15 Univ College Cork Nat Univ Ie Herstellungsverfahren von planaren wellenleitern

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0881526A (ja) * 1994-09-16 1996-03-26 Dainippon Ink & Chem Inc 光重合性樹脂組成物
US5945489A (en) * 1997-09-19 1999-08-31 Ashland, Inc. Liquid oligomers containing unsaturation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0881526A (ja) * 1994-09-16 1996-03-26 Dainippon Ink & Chem Inc 光重合性樹脂組成物
US5945489A (en) * 1997-09-19 1999-08-31 Ashland, Inc. Liquid oligomers containing unsaturation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 07 31 July 1996 (1996-07-31) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022043180A1 (fr) 2020-08-28 2022-03-03 Basf Se Procédé de séchage uv de dispersions de peinture de polyuréthane à base d'eau sans initiateurs de surface pouvant être activés par uv-c

Also Published As

Publication number Publication date
AU1024501A (en) 2001-04-23
DE19949383A1 (de) 2001-04-19

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