WO1999018134A1 - Revetements durcis aux uv contenant des amino-alcools tertiaires - Google Patents

Revetements durcis aux uv contenant des amino-alcools tertiaires Download PDF

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Publication number
WO1999018134A1
WO1999018134A1 PCT/US1998/019647 US9819647W WO9918134A1 WO 1999018134 A1 WO1999018134 A1 WO 1999018134A1 US 9819647 W US9819647 W US 9819647W WO 9918134 A1 WO9918134 A1 WO 9918134A1
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Prior art keywords
tertiary amino
amino alcohol
composition
acrylated
dimethylamino
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PCT/US1998/019647
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English (en)
Inventor
Marina D. Hoffman
Nancy F. Farrington
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Angus Chemical Company
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Priority to AU94017/98A priority Critical patent/AU9401798A/en
Publication of WO1999018134A1 publication Critical patent/WO1999018134A1/fr

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    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • This invention relates generally to the radiation curing of coatings, inks and overprint varnishes, particularly by ultraviolet (UV) radiation. More particularly, it relates to the improvement of the photoinitiators and co-initiators used to advance the polymerization of such coatings. The invention improves both the extent of polymerization and the speed with which it occurs.
  • UV radiation ultraviolet
  • UV or electron beam (EB) energy facilitates the cross-linking of curable compositions by exposing them to ultraviolet (UV) or electron beam (EB) energy.
  • UV-curable coatings and inks have gained widespread acceptance because of improved performance. They also have advantages over competing conventional technologies with regard to energy cost and environmental impact.
  • Conventional coatings and inks combine resins with volatile solvents which are removed by evaporation. This consumes energy and releases undesirable volatile organic compounds.
  • coatings and inks which are cured by UV or EB radiation eliminate the need for volatile solvents since reactive monomers are used instead. These do not have to be evaporated because they polymerize when exposed to radiation and become part of the cured film. Consequently, the energy consumption is reduced, and the volatile organic emissions are reduced or eliminated.
  • UV and EB are the most commonly used. EB curing requires high voltages to produce electrons which are capable of polymerizing without needing photoinitiators. UV curing requires low energy, typically supplied by mercury vapor lamps, but requires photoinitiators to initiate polymerization. UV curing is often favored over EB curing because of lower installation costs.
  • UV curing involves rapid polymerization of reactive unsaturated compounds.
  • the principal components of UV cured coatings, inks and overprint varnishes are typically acrylated oligomers, multifunctional acrylates, and monofunctional monomers.
  • Photoinitiators are typically alpha cleavage (type I) initiators such as benzoin ethers, benzil ketals, or acetophenones, or hydrogen abstraction (type II) initiators such as benzophenone, thioxanthone, and derivatives thereof.
  • Co-initiators also called accelerators or synergists
  • tertiary amines are often used, particularly tertiary amines, and tertiary amino alcohols.
  • U.S. Patent No. 3,772,062 discloses and claims coating compositions comprising various acrylates cured by ultraviolet radiation and using as photoinitiators benzophenone and related ketones with methyl diethanolamine (MDEA).
  • MDEA methyl diethanolamine
  • U.S. Patent No. 3,966,574 discloses the use of certain food grade dyes as photoinitiators and an alkanolamine, particularly MDEA, as an "activator.”
  • U.S. Patent No. 4,054,719 discloses a new photosensitizer, a phenacyl acetate, and a tertiary aliphatic amine used to cure, by ultraviolet radiation, a photopolymerizable composition.
  • U.S. Patent No. 4,054,721 also discloses a new photosensitizer which is complimented by a tertiary aliphatic amine, exemplified by MDEA.
  • U.S. Patent No. 4,395,539 discloses a glycol containing a tertiary amine group, which is a component of an aromatic polyester.
  • the polyester is combined with a photopolymerizable compound and a photoinitiator, such as an aromatic ketone.
  • EP Patent No. 0434 098 A2 discloses a photocurable composition which includes a multifunctional amine as defined therein and an aromatic ketone photoinitiator.
  • CA 1,224,182 discloses the use of a photoinitiator including a ketone and a hindered amine. Benzophenone and related compounds are listed as suitable ketones, and MDEA and related alkanol amines are listed as suitable hindered amines.
  • German Patent No. DE 4222576 discloses a UV hardened ink formulation which includes at least two amines as accelerators, at least one of which is a tertiary amine.
  • DOC depth of cure
  • MDEA methyl diethanol amine
  • the invention is a radiation-curable composition which includes a photopolymerizable formulation comprising oligomers and multifunctional and monofunctional monomers, at least one photoinitiator, and a tertiary amino alcohol having formula
  • Ri and R 2 are methyl
  • R 3 is hydrogen or C ⁇ - C 5 alkyl
  • R is - C 5 alkyl or - CH 2 OH
  • R 5 is C1-C 5 alkyl substituted with at least one hydroxyl group.
  • the invention is an improved method of radiation curing compositions in the presence of a photoinitiator and a tertiary amine where the tertiary amine is a tertiary amino alcohol having the formula
  • Ri and R 2 are methyl, R 3 is hydrogen or C ⁇ - C 5 alkyl , R is C ⁇ - C 5 alkyl or -
  • R 5 is C ⁇ -C 5 alkyl substituted with at least one hydroxyl group.
  • the tertiary amino alcohols of the invention may be used with both type I and type II photoinitiators.
  • type II photoinitiators are shown to provide increased depth of cure, increased surface cure, or both. Such results permit increased productivity, chemical resistance, and reduced cost in commercial applications of the invention.
  • the tertiary amino alcohol may be -pre-reacted with a polymer so that it becomes part of the cured film.
  • Photopolymerizable Compounds Compounds which are useful in connection with the present invention, in general, are ethylenically unsaturated and polymerizable by radiation. In typical commercial practice, such compounds are cured by ultraviolet radiation having wavelengths in the range of about 200-450 nm. As previously discussed, UV cured coatings are typically comprised of acrylated oligomers, multifunctional acrylates, and monofunctional acrylates, although other types of polymerizable compounds may be used. Typically, acrylated oligomers are blended with multifunctional acrylates and monofunctional acrylates to form a UV curable composition. The oligomers and monomers are selected to provide the desired film properties.
  • oligomers are acrylated epoxies, acrylated aliphatic and aromatic urethanes, acrylics, and acrylated polyesters.
  • Multifunctional monomers are typically of two types, acrylates and methacrylates. While acrylates cure readily by UV or EB radiation, methacrylates usually require EB energy to initiate polymerization. Examples of multifunctional acrylate monomers include tripropylene glycol diacrylate (TRPGDA), trimethylol propane triacrylate (TMPTA), and the alkoxylated forms of TMPTA, such as TMPTAEO and TMPTAPO. These materials dilute the high viscosity acrylated oligomers and form about 20-60% of the coating formulation.
  • TRPGDA tripropylene glycol diacrylate
  • TMPTA trimethylol propane triacrylate
  • TMPTAEO and TMPTAPO alkoxylated forms of TMPTA
  • Trifunctional monomers such as TMPTA, increase the crosslink density, hardness, and solvent resistance of the coating formulation, while difunctional monomers such as TRPGDA, reduce viscosity, increase flexibility and impact resistance, and improve adhesion.
  • TMPTA Trifunctional monomers
  • TRPGDA difunctional monomers
  • These polymerizable materials are selected and blended to provide cured coatings having the desired balance of properties.
  • Monofunctional monomers are often chosen as diluents in coatings, inks and overprint varnishes to reduce viscosity, increase flexibility, and enhance adhesion by reducing coating shrinkage during cure.
  • examples of such monomers are vinyl acetate, vinyl pyrrolidone, phenoxyethylacrylate, and isobornyl acrylate.
  • the curable formulation of the invention may also include additional polymers and monomers, pigments, fillers, initiators, amines and adjuvants.
  • Suitable radiation-curable compounds useful in the invention are acrylated bisphenol A, diglycidyl ether and derivatives, acrylated epoxy novolacs, acrylated aromatic (TDI- and MDI-based) urethanes, acrylated aliphatic (IPDI-, HMDI-, and HDI-based) urethanes, which can be combined with monomers such as tripropylene glycol diacrylate (TRPGDA), trimethylolpropane triacrylate (TMPTA), and alkoxylated forms of TMPTA, such as TMPTAEO and TMPTAPO.
  • TRPGDA tripropylene glycol diacrylate
  • TMPTA trimethylolpropane triacrylate
  • TMPTAEO and TMPTAPO alkoxylated forms of TMPTA
  • Photoinitiators And Accelerators are essential in UV curing. When irradiated, they provide free radicals which initiate polymerization. The mechanisms by which this occurs are described by Oster, G., and Yang, N.L., in Chem. Rev., 68, No. 2, p. 125 (1968). One mechanism involves a photochemically induced homolytic fragmentation (type I) of the excited photoinitiator into free radicals. Examples of materials which respond to the UV radiation in this manner are benzoin ethers, benzyl ketals, and acetophenones and derivatives. Specific commercial examples are isobutyl benzoin ether and hydroxycyclohexylphenyl ketone.
  • Another mechanism involves electron excitation of an initiator from a ground state singlet to an excited triplet followed by electron transfer to a hydrogen atom donor to generate free radicals.
  • hydrogen abstraction (type II) initiators are benzophenone, thioxanthone, and their related compounds or derivatives, with amines.
  • Bimolecular hydrogen abstraction is a typical reaction of aromatic ketones and is limited to the type II photoinitiators.
  • Triplet state excited aromatic ketones do not undergo alpha cleavage reactions, although the first type of photoinitiator does. They can. however, extract a hydrogen atom from a suitable hydrogen donor.
  • Three factors are considered to govern the hydrogen abstraction; the triplet state configuration of the ketone. the triplet state energy of the ketone, and the bond strength of the carbon- hydrogen bond to be broken.
  • an efficient co-initiator such as an amine. is necessary. While amines are known to react via hydrogen abstraction, under certain conditions, they may also initiate polymerization via electron transfer.
  • Electron transfer processes are common in photochemistry, and a large number of bimolecular photoinitiating systems react via a photoinduced electron transfer process.
  • One of these systems is the aromatic ketone-amine combination.
  • Electron transfer to the excited triplet state produces a radical ion pair, which undergoes a proton transfer from the carbon alpha to nitrogen to the ketyl radical anion.
  • the acidity of the ⁇ -protons in amines is enhanced after one electron oxidation of the nitrogen, so that very fast proton transfer efficiently competes with back electron transfer.
  • Type II photoinitiators in common use include benzophenone, 2,4,6- trimethylbenzophenone, 3,3-dimethyl-4-methylbenzophenone, and thioxanthone and derivatives (e.g., 2,4-dimethylthioxanthone and 4-isopropylthioxanthone).
  • benzophenone When exposed to UV light, benzophenone is excited to its singlet state, followed by intersystem crossing to the triplet state. Since alpha cleavage is not likely because the energy is insufficient, free radical species are generated in the presence of a tertiary amine via a charge transfer complex (exiplex). Amines are good hydrogen donors for benzophenone because they have a strong affinity for the long lived benzophenone triplet state. The resulting radical is responsible for the initiation reaction, the benzhydril radical will likely dimerize to a benzpinacol compound.
  • Initiators are inactivated by oxygen because the aminoalkyl radical can react with oxygen to form a peroxide that can generate another amino radical via hydrogen abstraction.
  • compositions containing benzophenone-amine initiator systems are usually less sensitive to oxygen inhibition. This oxygen consumption effect makes photopolymerization of a thin film very efficient.
  • the most commonly used amine is n- methyldiethanol amine (MDEA), although other aliphatic and aromatic amines have been used.
  • Tertiary amines can fill two roles in UV curing by a free radical route. They can scavenge peroxy intermediates formed by the reaction of oxygen with radical sites or, as the aminoalkyl/radicals, they can react with oxygen, thus reducing the retarding effect of oxygen on the cure rate. Possible mechanisms for oxygen scavenging reactions between amines, excited amines, and amine radicals with oxygen have been discussed by many authors, including Dietliker, K. K., "Chemistry And Technology Of UV And EB Formulations For Coatings, Inks, And Paints," 3rd ed., SITA Technology, Ltd., London, UK (1991), pp. 83-86.
  • the present invention employs tertiary amino alcohols as co-initiators, particularly for type II photoinitiators, although they may be used also with type I photoinitiators.
  • the polymerization is advanced for coatings, inks and overprint varnishes using photoinitiators and tertiary amino alcohols of the invention compared to the previous coatings, inks and overprint varnishes.
  • the depth of cure, the surface cure, or both are improved with type II photoinitiators, as will be seen in the
  • the tertiary amino alcohols of the invention are particularly useful with thick or pigmented coatings or inks since they can increase the depth of cure, thus reducing the need to use the more expensive alpha cleavage (type I) photoinitiators, which have been considered to provide superior through cure.
  • the tertiary amino alcohols, in combination with the photoinitiators, also can improve the surface cure. It has been claimed by other workers in the field that hydrogen abstraction initiators (type II) in combination with amines gave improved surface cure, but poorer depth of cure.
  • Amines in general have been used as co-initiators with the type II initiators (e.g., aromatic ketones) to improve surface cure by reducing oxygen inhibition of the polymerization at the surface of the film, as discussed above.
  • the preferred commercial amine co-initiator is N-methyldiethanol amine (MDEA).
  • MDEA N-methyldiethanol amine
  • the Examples below will compare MDEA with tertiary amino alcohols of the present invention.
  • the co-initiator tertiary amino alcohols of the present invention are those defined by the formula
  • R 2 4 where Ri and R 2 are methyl, R 3 is hydrogen or Ci - C 5 alkyl, R is C t - C 5 alkyl or - CH 2 OH, and R 5 is C 1 -C 5 alkyl substituted with at least one hydroxyl group.
  • tertiary amino alcohols examples include, but are not limited to, 2- dimethylamino-1-butanol (DMAB), 2-dimethylamino-2-ethyl-l,3-propanediol
  • DMAEPD 2-dimethylamino-2-methyl-l-propanol
  • DAMPD 2-dimethylamino-2- methyl-l,3-propanediol
  • the amount of the tertiary amino alcohol used in a UV curable formulation will be in the range of about 1-15 wt.%.
  • the tertiary amino alcohols will be mixed with the reactive oligomers and monomers, along with the photoinitiator, before curing.
  • Another method of using the tertiary amino alcohols is to pre-react them with a polymer so that they become part of the polymer backbone and, in turn, of the cured coating.
  • the tertiary amino alcohol would be pre-reacted with a radiation curable polymer, then mixed with other reactive compounds, such as acrylates, and then radiation cured.
  • photopolymerizable mixtures are formulated with benzophenone (BP) as the photoinitiator and with MDEA and the tertiary amino alcohols of the invention listed above as accelerators.
  • BP benzophenone
  • MDEA tertiary amino alcohols of the invention listed above as accelerators.
  • the compositions reported in the Tables refer to the ratio of the acrylated oligomer to the acrylate monomer, but the actual formulas are as follows.
  • Ebecryl® 8402 (acrylated aliphatic urethane)90g
  • Ebecryl® 1701 (acrylic oligomer) 70g
  • the Ebecryl® oligomers are products of UCB Radcure.
  • the depth of cure results were determined in the following manner. After preparing the formulations, they were drawn down on a depth of cure comparator having a channel graduated from 1-125 mils. The film was then cured by passing the coated substrate through a Fusion System LC-6 UV processor equipped with one F300S6, H bulb. 156 cm module. The processor speed was 20 ft./min., which irradiated the coating with 945 mj/c ⁇ T. The uncured (liquid) portion of the coating was blotted off with a paper towel, and the polymerized film was measured at its thickest section with a
  • Mitutoyo digimatic gauge The thickness of the polymer films were reported as depth of cure (DOC) in thousandths of an inch. This test is one way of determining the efficiency of initiator systems in thick or pigmented coatings.
  • the surface cure was measured by determining the chemical resistance using the double rub MEK (methyl ethyl ketone) method.
  • the films were drawn down on Leneta N2A charts using a #8 wire rod to give a dry film thickness of 0.3-0.4 mils.
  • the films were irradiated in the UV processor described above using belt speeds of 16 - 100 ft./min. The belt speed used was dependent on the oligomer system used.
  • the cured films were double rubbed with the MEK soaked swabs until the swab broke through the film. The number of rubs required was recorded as an indication of the completeness of the cure. It was assumed that full cure was achieved when 200 double rubs with MEK did not break through the film. Then, the belt speed was increased gradually until 200 double MEK rubs were no longer achieved, and differences between the tertiary amine co-initiators were evident. The data reported reflects the speeds at which differences were evident, but as close as possible to full cure.
  • Example 1 The acrylated epoxy oligomer (Ebecryl® 3700) was formulated with each of four multifunctional monomers, tripropylene glycol diacrylate (TRPGDA), trimethylolpropane triacrylate (TMPTA), ethoxylated trimethylolpropane triacrylate (TMPTAEO), and propoxylated trimethylolpropane triacrylate (TMPTAPO).
  • TRPGDA tripropylene glycol diacrylate
  • TMPTA trimethylolpropane triacrylate
  • TMPTAEO ethoxylated trimethylolpropane triacrylate
  • TMPTAPO propoxylated trimethylolpropane triacrylate
  • BP Benzophenone
  • Example 2 The experiment of Example 1 was repeated using a different oligomer, Ebecryl® 8402, an acrylated aliphatic urethane.
  • the results are reported in Table II.
  • Table II shows, for coatings containing TRPGDA and TMPTA, two of the tertiary amino alcohols (DMAB and DMAMP) provided greater depth of cure than coatings containing MDEA.
  • the coating containing DMAEPD was equivalent to that containing MDEA, while DMAMPD was slightly worse.
  • For coatings including the monomer TMPTAEO only those containing DMAB gave a greater depth of cure, while with the coatings made with the monomer TMPTAPO, all of the tertiary amino alcohols of the invention showed greater depth of cure than those made with MDEA.
  • Example 1 The experiment of Example 1 was repeated again using another oligomer Ebecryl® 4827, an acrylated aromatic urethane. The results are reported in Table III.
  • Example 1 The experiment of Example 1 was repeated using still another oligomer.
  • the acrylated polyester. Ebecryl® 40 was formulated without monomers, but with the same five benzophenone/tertiary amino alcohol initiator systems used in Examples 1-4.
  • DMAB and DMAMP amines provided a greater depth of cure than the control, MDEA.
  • DMAEPD provided the same depth of cure and DMAMPD somewhat poorer depth of cure.
  • An acrylated epoxy oligomer, Ebecryl® 3700 was formulated with each of the four acrylated monomers and each of the five tertiary amino alcohols used in the previous experiments.
  • the films were cured at various belt speeds and then tested using the double rub (with MEK) method previously described.
  • the speed of the UV processor was adjusted to provide a full cure, i.e., 200 double MEK rubs, and then the belt speed was increased by 10 ft./min. to determine differences between tertiary amines. The results are reported in Table VI.
  • the initiator packages BP/DMAB and
  • the coated films were cured and tested as in Example 6. In this test, the slowest speed available on the UV processor was used, since the oligomer is inherently slow curing. A full cure (i.e., 200 double MEK rubs) was not achieved, but some differences were apparent. The results are reported in Table VII.
  • Example 6 An acrylated aromatic urethane oligomer, Ebecryl® 4827, was formulated as in Example 6 and tested in the same manner. The results are reported in Table VIII. The speed of the UV processor was adjusted in a similar manner as in Example VI. except that for formulations containing TMPTAPO, the lowest speed was used as in Example 7.
  • all the BP/tertiary amino alcohol packages improved the surface cure of the films, except for BP/DMAMP, when compared to the BP/MDEA control.
  • all the BP/tertiary amino alcohol packages of the present invention improved the surface cure.
  • all of the BP/tertiary amino alcohol packages improved surface cure, except for the BP/DMAB combination.
  • Example 6 An acrylic oligomer, Ebecryl® 1701, was formulated and tested as in Example 6. The speed of the UV processor was adjusted as in Example 6, except for the formulation containing TRPGDA for which 200 MEK double rubs were never achieved. It was cured at the slowest possible speed, but differences in surface cure were found. The results are reported in Table IX.
  • BP/DMAMP and BP/DMAMPD were inferior to BP/MDEA.
  • TMPTAEO TMPTAEO
  • All of the BP/tertiary amino alcohol initiator packages provided improved surface cure compared to the BP/MDEA control.
  • DMAEPD 2-dimethylamino-2- ethyl-1,3 propanediol
  • DMAMP 2-dimethylamino-2-methyl-l-propanol
  • MAEPD and DMAMPD (2-dimethylamino-2-rnethyl-l,3 propanediol) are able to provide significant improvements in surface cure compared to the MDEA control. Improved surface cure allows the formulator flexibility to decrease the initiator package while retaining adequate cure. It also allows the user to increase line speeds, providing increases in productivity and/or reducing costs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
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Abstract

Une composition durcissable par rayonnement comprend des composés photopolymérisables, tels que des époxy, des uréthanes et des polyesters acryliques, ainsi que des photoinitiateurs tels que la benzophénone avec des amino-alcools tertiaires, tels que le 2-diméthylamino-1-butanol, en tant que co-initiateurs. Les co-initiateurs permettent d'améliorer la vitesse de durcissement, la profondeur de durcissement ou les deux. Les amino-alcools tertiaires de l'invention sont définis par la formule (I) dans laquelle R1 et R2 représentent méthyle, R3 représente hydrogène ou alkyle C1-C5, R4 représente alkyle C1-C5 ou -CH2OH, et R5 représente un alkyle C1-C5 substitué par au moins un groupe hydroxyle.
PCT/US1998/019647 1997-10-08 1998-09-21 Revetements durcis aux uv contenant des amino-alcools tertiaires WO1999018134A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1592778A2 (fr) * 2003-02-03 2005-11-09 Actinic, Inc. Compositions d'hormones juveniles et procedes de fabrication
FR2940657A1 (fr) * 2008-12-30 2010-07-02 Mgi France Composition de vernis pour substrat imprime par jet d'encre.

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4255464A (en) * 1977-12-30 1981-03-10 Akzo N.V. Method for the manufacture of objects from an unsaturated polyester composition
US4295947A (en) * 1978-09-18 1981-10-20 Hitachi Chemical Company, Ltd. Photo-curable coating compositions for building materials
US4499175A (en) * 1981-11-03 1985-02-12 Sericol Group Limited Photopolymerizable materials for use in producing screen printing stencils
US4522465A (en) * 1983-11-10 1985-06-11 Desoto, Inc. Optical fiber coated with an ultraviolet cured topcoating
US4537667A (en) * 1984-04-25 1985-08-27 Desoto, Inc. Radiation-curable copolymers of monoethylenic monomers
US4990364A (en) * 1986-12-04 1991-02-05 501 Schmalbach Lubeca Ag Solvent-free, low-monomer or monomer-free polymerizable hot melt coating process
US5068153A (en) * 1988-06-27 1991-11-26 E. I. Du Pont De Nemours And Company Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a phosphonium catalyst
US5070121A (en) * 1988-04-26 1991-12-03 Schmalbach Lubeca Ag Solvent-free, low-monomer or monomer-free polymerizable hot melt composition
US5380772A (en) * 1989-12-11 1995-01-10 G-C Toshi Kogyo Corporation Modelling liquid for dental porcelain
US5679722A (en) * 1993-07-15 1997-10-21 Teijin Seiki Co., Ltd. Resin composition for production of a three-dimensional object by curing

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4255464A (en) * 1977-12-30 1981-03-10 Akzo N.V. Method for the manufacture of objects from an unsaturated polyester composition
US4295947A (en) * 1978-09-18 1981-10-20 Hitachi Chemical Company, Ltd. Photo-curable coating compositions for building materials
US4499175A (en) * 1981-11-03 1985-02-12 Sericol Group Limited Photopolymerizable materials for use in producing screen printing stencils
US4522465A (en) * 1983-11-10 1985-06-11 Desoto, Inc. Optical fiber coated with an ultraviolet cured topcoating
US4537667A (en) * 1984-04-25 1985-08-27 Desoto, Inc. Radiation-curable copolymers of monoethylenic monomers
US4990364A (en) * 1986-12-04 1991-02-05 501 Schmalbach Lubeca Ag Solvent-free, low-monomer or monomer-free polymerizable hot melt coating process
US5070121A (en) * 1988-04-26 1991-12-03 Schmalbach Lubeca Ag Solvent-free, low-monomer or monomer-free polymerizable hot melt composition
US5068153A (en) * 1988-06-27 1991-11-26 E. I. Du Pont De Nemours And Company Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a phosphonium catalyst
US5380772A (en) * 1989-12-11 1995-01-10 G-C Toshi Kogyo Corporation Modelling liquid for dental porcelain
US5679722A (en) * 1993-07-15 1997-10-21 Teijin Seiki Co., Ltd. Resin composition for production of a three-dimensional object by curing

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1592778A2 (fr) * 2003-02-03 2005-11-09 Actinic, Inc. Compositions d'hormones juveniles et procedes de fabrication
EP1592778A4 (fr) * 2003-02-03 2008-06-11 Ashland Licensing & Intellectu Compositions d'hormones juveniles et procedes de fabrication
US7977305B2 (en) 2003-02-03 2011-07-12 ProvisionGard Technology LLC Juvenile hormone compositions and methods for making same
FR2940657A1 (fr) * 2008-12-30 2010-07-02 Mgi France Composition de vernis pour substrat imprime par jet d'encre.
EP2204401A1 (fr) * 2008-12-30 2010-07-07 Mgi France Composition de vernis pour substrat imprimé par jet d'encre
US8822562B2 (en) 2008-12-30 2014-09-02 M.G.I. Usa, Inc. Ink-jet printer ink

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