EP1002018A2 - Compositions durcissables par rayonnement - Google Patents

Compositions durcissables par rayonnement

Info

Publication number
EP1002018A2
EP1002018A2 EP98943876A EP98943876A EP1002018A2 EP 1002018 A2 EP1002018 A2 EP 1002018A2 EP 98943876 A EP98943876 A EP 98943876A EP 98943876 A EP98943876 A EP 98943876A EP 1002018 A2 EP1002018 A2 EP 1002018A2
Authority
EP
European Patent Office
Prior art keywords
composition according
anyone
acid
composition
polyester
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Withdrawn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
EP98943876A
Other languages
German (de)
English (en)
Inventor
Mingxin Fan
Gary W. Ceska
James Horgan
Nicholas Trainer
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.)
Sartomer Co Inc
Original Assignee
Sartomer Co Inc
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
Priority claimed from US08/910,641 external-priority patent/US6030703A/en
Application filed by Sartomer Co Inc filed Critical Sartomer Co Inc
Publication of EP1002018A2 publication Critical patent/EP1002018A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

Definitions

  • This invention relates to radiation curable unsaturated polyester coating compositions, processes for coating a surface with such compositions, and the resultant coated articles.
  • Radiation cure has become more and more popular in industry due to its high cure speed, and relatively low or no VOC (Volatile Organic Compounds).
  • (Meth) aerylate monomers and oligomers are the most prevalent radiation curable compositions, and are typically cured in the presence of free radical initiators and electron beam or ultraviolet light (UV) radiation.
  • UV ultraviolet light
  • cationic systems have been developed for cationic cure, these systems are based on cycloepoxide, vinyl ethers. Cationic systems are not inhibited by oxygen, therefore no nitrogen blanket is needed.
  • Radiation curable compositions based on unsaturated polyesters and vinyl ethers have been disclosed, for example by Friedlander, et al, U.S. Patent 5,536,760, assigned to PPG Industries, Inc., wherein radiation curable compositions based on unsaturated polyesters and compounds having at least two vinyl ether groups are shown ; U.S. Patent 5,334,456 which disclosed free radical curable compositions based on saturated backbone with terminal maleate or fumarate and vinyl ethers ; U.S. Patents 5,334,455 and 5,340,653, which disclosed saturated backbone with maleate or fumarate terminal groups and vinyl ethers ; Johnson, et al, U.S. Patent 5,446,073, assigned to Fusion Systems Corporation, which disclosed UV photopolymerization processes employing a charge transfer complex without a photoinitiator.
  • U.S. Patents 5,340,653 ; 5,334,456 and 5,334,455, assigned to Stamicarbon, B.V. teach free radical radiation curable compositions comprising vinyl ether compound containing 1 to 6 vinyl ether groups ; maleate and/or fumarate end group-containing urethane polymer.
  • the maleate/fumarate can be a half ester with epoxy functional compound, or the maleate/fumarate can be end groups on a saturated backbone.
  • the object of the aforementioned Stamicarbon patents is flexibility compared to the aforementioned PPG Industries patent.
  • vinyl ether would not be understood to those skilled in the art as including propenyl ethers, the Stamicarbon patents define their vinyl ethers by a structural formula which would encompass propenyl ethers ; however, no working examples using propenyl ethers were presented in the Stamicarbon patents.
  • Propenyl ethers have been developed for cationic cure, but have not been specifically suggested for free radical, radiation cured copolymerization with internally unsaturated polyester coating compositions.
  • U.S. Patents 4,749,807 ; 4,845,265 ; 5,286,835 disclosed vinyl ether terminated ester oligomers which included propenyl ethers ;
  • U.S. Patent 4,775,732 disclosed vinyl ether terminated ester and urethane resins.
  • U.S. Patent 5,153,237 described urethane based propenyl ethers for cationic cure ; Crivello has disclosed some propenyl monomers in U.S.
  • Patent 5,567,858 based on cyclic ethers, polyethers, and alkane ⁇ . Radiation curable compositions have been disclosed in U.S. Patent 5,055,357. Although propenyl ethers have been developed in recent years discussed above, they have been mainly used in the cationic polymerizations as disclosed in U.S. Patents 5,567,858 ; 5,055,357 ; 5,286,835 ; 4,845,265 and 4,775,732. Propenyl ethers were mentioned as a possible electron donor for the formation of charge transfer complexes for photopolymerization in U.S.
  • Patent 5,446,073 due to the steric effect of the methyl group in the propenyl ethers, the real cure rate is dependent on the electron acceptor. With an unsaturated polyester as electron acceptor, no practical cure rate can be obtained without photoinitiator according to the 5,446,073 patent.
  • Propenyl ethers are typically mixtures of different isomers, each propenyl ether group has two possible isomers depending on the methyl group configuration. Due to the steric effect of the methyl groups in the propenyl ether molecules, they are expected to be much less reactive than their vinyl ether analogs, and therefore in most cases vinyl ethers are preferred as in the aforementioned Stamicarbon patents. Prior to this invention, it was expected that no practical cure rate can be obtained with propenyl ethers.
  • the invention comprises a composition suitable for radiation curable coatings comprising at least one polyester having unsaturated backbone and at least one compound having one to six propenyl ether groups.
  • the invention comprises a method of coating a surface of an article comprising applying a such composition to the surface and curing said composition with electron beam or UV radiation.
  • a still further aspect is the resultant coatings and coated articles, prepared by this method of coating.
  • propenyl ethers are as reactive as vinyl ethers when used in combination with unsaturated polyesters containing internal unsaturation such as from maleate / fumarate, maleimide, maleimide / maleate / fumarate in a radiation curable coating composition.
  • Suitable unsaturated polyesters with internal unsaturation for use in the invention include, for example, the reaction product of at least one unsaturated compound selected from aleic acid, fumaric acid, maleic anhydride, maleimide, and itaconic acid with at least one polyol.
  • the polyol can be, for example ethylene glycol, diethylene glycol, propylene glycol, glycerol, 1,4-butane glycol, 1,6-hexane diol, l,2-bis(hydroxy ethyl) cyclohexane, and/or trimethylol propane. Diols are preferred.
  • phthalic acid isophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, succinic acid, glutaric acid, succinic anhydride, and/or phthalic anhydride can be used.
  • saturated organic acid such as phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, succinic acid, glutaric acid, succinic anhydride, and/or phthalic anhydride can be used.
  • One particularly preferred polyester is the reaction product of maleic anhydride, 1,4-butane diol, and 1- butanol.
  • Another suitable polyester has internal unsaturation and terminal maleimide groups.
  • the equivalent ratio of the compound having one to six propenyl ether groups to the polyester can be 5:1 to 1:5, preferably about 2:1 to 1:2, more preferably 1.2:1.0 to 0.8:1.0. For most coating purposes, it is desirable that the relative ratio is about 1:1 to avoid excess propenyl ethers which may cause plasticizing effect.
  • the coating compositions can be cured by known radiation methods, usually UV or electron beam radiation.
  • the photoinitiator is preferably present for UV curable versions, but for electron beam curable versions, no photoinitiator is generally used.
  • the method of coating a surface of an article includes applying a liquid composition comprising the polyester, the propenyl ether, and any photoinitiator and/or other additives to the surface of the article, and curing the composition with electron beam or UV radiation.
  • the resulting coating is cured via free radical polymerization initiated by the radiation and the optional photoinitiator.
  • Suitable articles which can be coated are any which are typically coated using radiation cure technology, for example articles in the form of coated glass fiber.
  • Another aspect of the invention concerns a crosslinked polymer prepared by curing a composition of the invention with electron beam or UV radiation.
  • One particular advantage of the invention is the fact that the propenyl ethers are generally easier to prepare than their corresponding vinyl ethers which were used in the prior art.
  • the propenyl ethers are simply prepared by iso erization of the corresponding allyl ether.
  • Propenyl ether functional group containing compounds used in this invention can be saturated or unsaturated for their backbone and the backbones can be alkane ⁇ , polyethers, polyesters, urethanes, polyether polyesters. They can be monofunctional , difunctional or multifunctional.
  • Propenyl ethers can be prepared based on the prior art discussed above, they can also be prepared, as shown in the example section, from alkoxylated allyl alcohols, followed by catalytic double bond isomerization.
  • Preferred propenyl ethers having one to six propenyl ether groups include ethoxylated hexane diol dipropenyl ether, trimethylol propane dipropenyl ether, tetraethylene glycol dipropenyl ether, and cyclohexane dimethanol dipropenyl ether.
  • the optional photoinitiators used in the invention include benzoin ethers, benzil ketals, acetophenones, phosphine oxide, and benzophenone, as well as others which are known in the art. It is preferred to use a photoinitiator in a ratio of 1-10% by weight, when the composition is to be UV cured. When the composition is to be electron beam cured, a photoinitiator is not generally required.
  • a composition of the invention is liquid which can be cured by radiation such as electron beam or ultraviolet light (UV) .
  • the key components of the composition are compounds containing maleimide, maleate / fumarate and propenyl ether containing compounds, optionally, free radical photoinitiator may be present.
  • the maleimide, maleate / fumarate containing compounds are liquids, preferably unsaturated polyesters.
  • Maleate / fumarate functional groups may be at the terminal or backbone, when maleimide functional groups are present in the molecules they are at the chain terminals.
  • These compounds can be unsaturated polyester polymers or unsaturated polyester oligomers or a mixture thereof.
  • the preparation of these unsaturated polyesters from polycarboxylic acid or anhydride with polyhydric alcohol is well known in the art. Since the compositions are cured free radically, free radical polymerizable monomers and oligomers may be added.
  • Some monomer and oligomer examples are hexanediol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tri ethylolpropane triacrylate, tripropylene glycol diacrylate, glycerol triacrylate, hexanediol dimethacrylate, glycidyl methacrylate, butyl acrylate, ethyl acrylate, and the like.
  • Vinyl ether compounds may also be present in combination with propenyl ethers.
  • a clear, low viscosity unsaturated polyester resin was obtained (702.0 g) .
  • the physical properties of the unsaturated polyester were as follows : Viscosity at 25 °C was 5.612 Pa.s (5612 cps) ; Density at 25°C was 1.2035 ; Mn was 1766 ; Mw was 1863 and Color was 17 APHA.
  • Ethoxylated allyl alcohol (3 moles EO, 260.0 g) , 1, 6-dibromohexane (144.0 g, 0.59 moles), toluene (100 ml), sodium hydroxide (60.0 g) , and tetrabutylammoniu hydrogen sulfate (1.0 g) were added to a reactor. The mixture was stirred and exothermic reaction was observed. The reaction mixture was stirred at 100 °C for seven hours followed by cooling down to room temperature. The cooled mixture was poured into 500 ml water, the organic layer was isolated and washed with three 200 ml water followed by filtration through filter paper. The light yellow clear solution was stripped at 90°C under reduced pressure (3.33-4.00 kPa (25-30 mmHg)). 180 g liquid was obtained.
  • trimethylolpropane diallyl ether (200.0 g) was isomerized to trimethylolpropane dipropenyl ether using ruthenium tris (triphenylphosphine) dichloride following the above procedure.
  • E289 was prepared according to the same procedure as E284 with maleic anhydride : 73.5 g , ethanol amine : 9.16 g and ethylene glycol : 46.5 g.
  • BMI is an aliphatic unsaturated bismaleimide resin obtained from Quantum Material Inc. as CM003.
  • TMPDPE is trimethylolpropane dipropenyl ether obtained from Example 3.
  • NC means not cured.
  • Darocure 1173 is a 2-hydroxy-2-methyl propiophenone photoinitiator obtained from CIBA Specialty Chemicals .
  • SR9003B is propoxylated neopentylglycol diacrylate available from Sartomer Company, Inc.
  • UPE is the unsaturated polyester obtained from Example 1.
  • DVE-3 is tetraethylene glycol divinyl ether obtained from ISP.
  • CHVE is cyclohexane dimethanol divinyl ether from
  • DPE is a dipropenyl ether from Example 2.
  • Maleimide, maleimide containing unsaturated polyester based formulation with vinyl ethers and propenyl ethers were prepared and cured following the procedure of Example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition appropriée pour un revêtement à radical libre et durcissable par rayonnement, laquelle comprend au moins un polyester à squelette insaturé et au moins un composé ayant de un à six groupes d'éther de propényle, et éventuellement, un photoinitiateur à radical libre. Le rapport équivalent entre les groupes d'éther de propényle et les groupes maléimide, maléate et/ou fumarate dans le polyester est, de préférence, de l'ordre de 5:1 à 1:5. Le procédé de durcissement de la composition consiste à exposer cette dernière à des rayonnements ionisants et/ou à une lumière ultraviolette. Les revêtements durcis et les articles enrobés ainsi obtenus sont aussi performants que leurs analogues à base d'éther de vinyle, mais les éthers de propényle sont plus faciles à préparer que leurs analogues à base d'éther de vinyle.
EP98943876A 1997-08-04 1998-07-24 Compositions durcissables par rayonnement Withdrawn EP1002018A2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US90530997A 1997-08-04 1997-08-04
US905309 1997-08-04
US08/910,641 US6030703A (en) 1997-08-13 1997-08-13 Radiation curable compositions comprising an unsaturated polyester and a compound having two to six-propenyl ether groups
US910641 1997-08-13
PCT/EP1998/004968 WO1999006463A2 (fr) 1997-08-04 1998-07-24 Compositions durcissables par rayonnement

Publications (1)

Publication Number Publication Date
EP1002018A2 true EP1002018A2 (fr) 2000-05-24

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98943876A Withdrawn EP1002018A2 (fr) 1997-08-04 1998-07-24 Compositions durcissables par rayonnement

Country Status (2)

Country Link
EP (1) EP1002018A2 (fr)
WO (1) WO1999006463A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50110193D1 (de) * 2000-01-24 2006-08-03 Altana Elec Insulation Gmbh Emissionarme Elektroisoliermassen
BR0113614A (pt) * 2000-09-05 2003-07-15 Dainippon Ink & Chemicals Composição de resina de poliéster insaturado
DE10144486C1 (de) * 2001-09-10 2003-04-24 Karlsruhe Forschzent Verfahren zum kontinuierlichen nichtthermischen Aufschluß und Pasteurisieren industrieller Mengen organischen Prozessguts durch Elektroporation und Reaktor zum Durchführen des Verfahrens

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL120556C (fr) * 1959-05-01
GB1188112A (en) * 1966-07-12 1970-04-15 Courtaulds Ltd Improvements in and relating to Surface Coating
JPS61174256A (ja) * 1985-01-30 1986-08-05 Nippon Shokubai Kagaku Kogyo Co Ltd 紫外線硬化型樹脂組成物
MX169697B (es) * 1987-12-28 1993-07-19 Ppg Industries Inc Mejoras a composiciones fraguables por radiacion basadas sobre poliesteres insaturados y compuestos teniendo por lo menos dos grupos de vinil eter
DE4022234A1 (de) * 1990-07-12 1992-01-16 Herberts Gmbh Verfahren zur herstellung von schutz-, hilfs- und isoliermaterialien auf faserbasis, fuer elektrische zwecke und optische leiter unter verwendung von durch energiereiche strahlung haertbaren impraegniermassen
JP3060088B2 (ja) * 1995-11-17 2000-07-04 三洋化成工業株式会社 光硬化型印刷インキ組成物
JP3060091B2 (ja) * 1995-11-20 2000-07-04 三洋化成工業株式会社 光ディスク用オーバーコート組成物
JP3060090B2 (ja) * 1995-11-20 2000-07-04 三洋化成工業株式会社 光硬化型金属コーティング剤
JP3172074B2 (ja) * 1995-11-21 2001-06-04 三洋化成工業株式会社 光ディスク用光硬化型組成物
SE506958C2 (sv) * 1996-06-20 1998-03-09 Mcwhorter Technologies Ab Fotopolymeriserbar polyesterkomposition samt lack eller färgformulering

Non-Patent Citations (1)

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Title
See references of WO9906463A3 *

Also Published As

Publication number Publication date
WO1999006463A2 (fr) 1999-02-11
WO1999006463A3 (fr) 1999-04-22

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