EP1003789A1 - Composition a base de resine, a durcissement ameliore par exposition a un rayonnement - Google Patents

Composition a base de resine, a durcissement ameliore par exposition a un rayonnement

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Publication number
EP1003789A1
EP1003789A1 EP98937870A EP98937870A EP1003789A1 EP 1003789 A1 EP1003789 A1 EP 1003789A1 EP 98937870 A EP98937870 A EP 98937870A EP 98937870 A EP98937870 A EP 98937870A EP 1003789 A1 EP1003789 A1 EP 1003789A1
Authority
EP
European Patent Office
Prior art keywords
resin composition
radiation
group
amine
curable resin
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Withdrawn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
EP98937870A
Other languages
German (de)
English (en)
Inventor
Aylvin Jorge Angelo Athanasius Dias
Johan Franz Gradus Antonius Jansen
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Publication of EP1003789A1 publication Critical patent/EP1003789A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/005—Dendritic macromolecules
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • the invention relates to a radiation- curable resin composition
  • a radiation- curable resin composition comprising a radiation- curable resin, a photo-excitable compound and an aliphatic amine.
  • Such a resin composition is known from Fouassier and Rabek, Radiation Curing in Polymer Science and Technology. Vol. Ill (1993), Chapter 5, pp. 153-176, which describes a radiation-curable resin composition containing a radiation-curable resin, a conjugated carbonyl compound, in particular benzophenone, as photo-excitable compound and an ethanol amine .
  • the combination of a photo-excitable compound and an amine is also called a Norrish type II radical initiator combination.
  • a Norrish type II combination is used to accelerate curing of a resin by means of, for instance, UV radiation.
  • the photo-excitable compound reacts with the amine, also called amine synergist, to form an amine radical which then initiates the polymerisation reaction.
  • ethanol amines are mentioned as the most excellent amine synergists, it also being stated that the reaction mechanism underlying the activity of the ethanol amines is unknown.
  • conversion in the framework of the present invention is understood to mean the fraction of the monomer compounds that is converted into polymer compounds upon curing after a certain time period. The conversion can be determined by means of, for instance, Photo-DSC measurements or Real Time - Fourier Transform Infra Red measurements .
  • the aim of the invention is to provide a radiation-curable resin composition that can be cured with a conversion that is higher than the state of the art conversion.
  • aliphatic amine is chosen a compound containing at least one tertiary amino group, at least one substituent of the tertiary amino group being an aliphatic chain containing at least one electron-withdrawing group.
  • the resin composition can be cured with a conversion that is superior to or at least equal to the state of the art conversion.
  • the resin composition according to the invention could be cured at an increased curing rate, which exceeds or at least equals the curing rate for the resin composition according to the state of the art.
  • a resin composition that can be cured with an increased conversion in combination with an increased curing rate is highly desirable .
  • a resin composition especially for dental applications, that can be easily cured and which shows no bad smell, comprising an aromatic or cyclic tertiary amine consisting of one tertiary amine group, of which one of the substituents is a cyanoethyl group.
  • curing rate is understood to be the ratio of the conversion (in %) over the curing time (in minutes or sec) , calculated in the first linear section of the curve representing the conversion versus the time for a resin composition that is being cured.
  • the aliphatic amine according to the invention is preferably a compound according to Formula 1
  • R 1 , R 2 and R 3 can each independently be chosen freely, it being understood that at least one of the substituents R 1 , R 2 and R 3 is equal to Z.
  • R 1 , R 2 and R 3 are aliphatic groups, for instance alkyl groups with for instance 1 to 100 atoms and alkenyl groups with for instance 2 to 100 atoms. Aliphatic groups are also understood to mean groups that contain one or more atoms that are not equal to carbon, for instance N, 0, S and P. Two substituents to be chosen from R 1 , R 2 and R 3 can also form part of a ring structure. Examples of such a ring structure are pyrrolidine and piperidine. It is also possible for a reactive unsaturation to be bound to the tertiary amine via R 1 , R 2 and R 3 .
  • Z is an aliphatic chain that contains an electron-withdrawing group.
  • the electron-withdrawing group can be chosen freely from the group of electron- withdrawing groups, for instance as listed in March, Advanced Organic Chemistry. 3rd Ed. (1985) p. 238, Table 1.
  • suitable electron-withdrawing groups are nitro groups, cyano groups, carboxy groups, oxycarbo ' yl groups, carbamoyl groups, formyl groups, sulpho groups, nitroso groups, oxo groups, alkenyl groups and alkynyl groups.
  • the electron- withdrawing group is a cyano group, a carboxy group or an oxycarbonyl group.
  • the aliphatic chain can be chosen freely.
  • Suitable aliphatic chains are alkyl, alkenyl and alkynyl chains, for instance methyl, ethyl, propyl or butyl chains.
  • the length of the aliphatic chain can be chosen freely ; however, the number of carbon atoms between the electron-withdrawing group and the N-atom on which the chain is substituted is preferably 1 to 20, more preferably 1 to 10, most preferably 1 to 5.
  • the aliphatic chain is also substituted, for instance with (hetero) aliphatic and (hetero) aromatic groups.
  • An example of such a substituted aliphatic chain is an isobutyl chain.
  • Suitable amines or compounds according to Formula 1 are alkyl amines, in which an electron withdrawing group is linked via an alkyl chain to the nitrogen atom of the tertiary amino group, for instance cyanoalkyl amines with an alkyl group of 1 to 5 carbon atoms, more preferably secondary or tertiary cyanoalkyl amines, for instance tris-(2- cyanoethyl) amine .
  • the amine is preferably a branched, highly branched or star-shaped dendrimer which contains at least one tertiary amino group and in which an electron-withdrawing group is linked to the nitrogen atom of the tertiary amino group via an alkyl chain.
  • suitable dendrimers are ester-terminated polyamidoamine dendrimers, for instance described in US-A-4507466, and nitrile-terminated polypropylene - imine dendrimers, for instance described in WO-A-93 14147 and WO-A-95 02008, or derivatives thereof, for instance esters, at least a portion of the terminal groups of the derivatives being an electron-withdrawing group .
  • nitrile-terminated polypropylene imine dendrimer chosen from the group consisting of:
  • ester- terminated polypropylene imine dendrimers chosen from the group consisting of the addition products of (meth) acrylates and polypropylene imine dendrimers; these addition products contain terminal groups that are (partially) modified with an oxycarbonyl group, for instance with a methyl acrylate or ethyl acrylate group.
  • the ester-terminated polypropylene imine dendrimers are chosen, for instance, from the group of the addition products of phenoxyethylacrylate and, respectively, the amino-terminated polypropylene amine dendrimers:
  • the ester-terminated addition products can for instance be obtained by addition of a (meth) acrylate, for instance phenoxyethylacrylate, to an amino-terminated polypropylene imine dendrimer.
  • a (meth) acrylate for instance phenoxyethylacrylate
  • the use of the addition products of a polypropylene imine dendrimer and a (meth) acrylate has the added advantage that the compatibility, for instance with regard to the solubility of the amine and the radiation-curable resin to be cured can simply be selected by means of the choice of the type of acrylate function.
  • a further advantage of polypropylene imine dendrimers and derivatives thereof that are suitable as amine according to the invention is that they contain a large amount of tertiary amino groups per weight unit of compound.
  • polypropylene imine dendrimers and derivatives thereof that are suitable as amine according to the invention is that the volatility of said dendrimers is lower than that of the state of the art amine synergists.
  • a low volatility is highly desirable as this facilitates handling and processing of the resin composition, for instance for safety and environmental considerations.
  • conjugated carbonyl compound is understood to mean a compound in which the carbonyl function is conjugated with one or more double bonds.
  • conjugated carbonyl compounds examples include benzophenone , xanthone , thioxanthone, ⁇ -keto-coumarine, aromatic 1, 2-diketones, maleimides, acridone, pyruvates, phenylglyoxalates or mixtures thereof.
  • Other suitable examples are chemical derivatives of these compounds, for instance substituted benzophenones and substituted thioxanthones as well as compounds containing more than one conjugated carbonyl compound and compounds in which two or more carbonyl compounds are conjugated with one another. It is obvious that Norrish type II combinations may comprise a combination of more than one photo-excitable compound and/or a combination of more than one amine .
  • the radiation-curable resin preferably contains a reactive unsaturation on an electron- withdrawing group (a) , optionally in combination with a reactive unsaturation on an electron-donating group (b) or an allyl group containing compound on an electron- donating group (c) or a mixture thereof (b+c) .
  • the reactive unsaturation on an electron- withdrawing group (a) is characterised by the structural element according to Formula 2
  • X is one of the following groups OR 7 , NR 7 R 8 or SR 7 .
  • R 4 , R 5 and R 6 can be chosen freely, independently of one another; suitable choices are: H, alkyl groups with 1 to 20 carbon atoms, aryl groups, COOR 9 , C0NR 9 R 10 , CH 2 COOR 9 , CH 2 OR 9 , OR 9 , NR 9 R 10 , SR 9 , Cl and CN.
  • R 7 , R 8 , R 9 and R 10 can be chosen freely, independently of one another; suitable choices are: H, alkyl groups with 1 to 20 carbon atoms (including linear and cyclic structures) , aryl groups, aromatic or aliphatic heterocyclic groups containing 0, S, N or P atoms, COY, CH 2 C0Y, CH 2 0Y, CH 2 NYZ, CH 2 SY, CH 2 CH 2 OY, CH 2 CH 2 NYZ, CH 2 CH 2 SY, CH 2 CH(CH 3 )OY, CH 2 CH (CH 3 ) NYZ , CH 2 CH (CH 3 ) SY, CH(CH 3 )CH 2 OY, CH(CH 3 )CH 2 NYZ, CH (CH 3 ) CH 2 SY, (CH 2 0) n Y, (CH 2 NZ) n Y, (CH 2 S) n Y, (CH 2 CH 2 0) n Y, (CH 2 CH 2 NZ) n Y, (CH 2 CH
  • n is an integer, for instance between 1 and 100.
  • Y and Z can be chosen freely, independently of one another; suitable choices are: H, alkyl groups with 1 to 20 carbon atoms (including linear and cyclic structures) , aryl groups and aromatic or aliphatic heterocyclic groups containing 0, S, N of P atoms.
  • the reactive unsaturation on an electron- donating group (b) is preferably chosen from the group comprising vinyl ethers, vinyl esters, vinyl amides, vinyl amines, vinyl thioethers and vinyl thioesters.
  • the compound comprising an allyl group on an electron-donating group (c) is preferably chosen from the group comprising allyl ethers, allyl ester, allyl amines or allyl amides.
  • the amount of reactive unsaturation on the electron-withdrawing group (a) of the radiation-curable resin is preferably between 25 and 100 mol%.
  • the amount of reactive unsaturation on an electron-donating group (b) or a compound comprising an allyl group on an electron-donating group (c) or a mixture thereof (b + c) of the radiation-curable resin before curing takes place is preferably between 0 and 75 mol%, depending on the amount of reactive unsaturation on an electron- withdrawing group (a) of the radiation-curable resin.
  • the amount of reactive unsaturation on an electron-withdrawing group (a) of the radiation-curable resin is 100 mol%. More preferably, the amount of reactive unsaturation on an electron-withdrawing group (a) of the radiation-curable resin is 50 mol% and the amount of reactive unsaturation on an electron-donating group (b) or a compound comprising an allyl group on an electron- donating group (c) or a mixture hereof (b+c) of the radiation-curable resin 50 mol%.
  • the reactive unsaturation on an electron- withdrawing group (a) can be linked to polymers or oligomers via R 7 .
  • polymers or oligomers are polyurethanes, polyesters, polyacrylates, polyethers, polyolefines, for instance polyethylene, polypropylene, polybutadiene, polystyrene, polysilicates, polycarbonates, polyvinylesters, rubbers, for instance polyisoprene, natural rubbers and polyepoxides and mixed polymers, for instance polyether urethanes, polyester urethanes, polyether carbonates and polyepoxide esters. Combinations of polymers or oligomers are other suitable examples.
  • the reactive unsaturation on the electron-withdrawing group (a) has, besides R 7, another functionality in the form of R 4 , R 5 or R 6 , for instance COOR 9 , CONR 9 R 10 , CH 2 COOR 9 or CH 2 OR 9 , then the reactive unsaturation can be incorporated in the polymer or oligomer chain.
  • examples of such polymers or oligomers are unsaturated polyesters in which fumarate, maleate, itaconate, citraconate or mesaconate functionalities have been incorporated.
  • the number of reactive unsaturations on an electron-withdrawing group on a polymer or oligomer is larger than 1.
  • the reactive unsaturation on an electron- donating group (b) or the compound comprising an allyl group on an electron-donating group (c) can be bound to the polymers or oligomers described above via ether, ester, amine or amide bonds, or, in the case of bifunctional reactive unsaturation on an electron- donating group or a bifunctional allyl compound, it can also be incorporated in a polymer or oligomer chain.
  • the radiation-curable resin can also contain low-molecular compounds with a reactive unsaturation.
  • These low- molecular compounds contain a reactive unsaturation in the molecule with substituents that may be of an aromatic, aliphatic or cycloaliphatic nature.
  • substituents may be of an aromatic, aliphatic or cycloaliphatic nature.
  • these molecules can contain various functionalities, i.e. be mono- and multifunctional.
  • radiation-curable resins that can be applied are based on, for instance, ethyl acrylate, ethyl methacrylate, methyl methacrylate, hexane diol diacrylate, hexane diol dimethacrylate, trimethylol propane triacrylate, trimethylol propane trimethacrylate, acrylamides, for instance acrylamide, N-methyl acrylamide, N-lauryl acrylamide, maleate esters, for instance ethyl maleate, diethyl maleate, methyl maleate, maleamides, for instance N,N'- bismaleamide, N,N' -dimethyl maleamide, maleimides, for instance maleimide, N-hexyl maleimide, fumarate esters, for instance ethyl fumarate, diethyl fumarate, fumaramides, itaconic acid esters, for instance methyl itaconate, dimethyl itaconate, ethyl itacon
  • the resin composition can also contain additives, for instance pigments, fillers and matting agents .
  • the amount of amine according to the invention that is applied in the resin composition can be chosen freely. In practice an amount between 0.1 and 15 wt.% is applied and the amount depends, inter alia, on the solubility of the amine in the resin composition. Preferably the amount of amine according to the invention is 1-10 wt.%, calculated relative to the total resin composition.
  • the amount of photo-excitable compound used can also be chosen freely. In practice an amount of between 0.1 and 15 wt.%, calculated relative to the total resin composition, is used.
  • the amount of photo- excitable compound used influences the conversion and the curing rate to a lower degree than the amount of amine according to the invention.
  • the radiation used for curing of the resin composition can be chosen from UV radiation, i.e. radiation at a wavelength of 0.6-380 nm, and electron beam (EB) radiation.
  • the amount of radiation used depends, inter alia, on the curing conditions, the resin composition and the specific application, and can be chosen freely by one skilled in the art.
  • Amines are generally used not only to serve as synergist, i.e. to initiate the reaction, but also as oxygen scavenger. Oxygen has an inhibiting effect, which can be decreased by the use of amines.
  • other amines may also be added which serve as synergist and/or as oxygen scavenger.
  • the resin composition may optionally also contain Norrish type I initiators.
  • these initiators radicals are generated by means of splitting-up of a molecule by the action of radiation.
  • these initiators which are mostly based on aromatic ketones, include: Darocure 1173 (TM) (2 -hydroxy-2 -methyl- 1-phenylpropane- 1- one as active component), Irgacure 184 ⁇ TM1 (hydroxy- cyclohexyl phenylketone as active component) , Irgacure 369 (TM) (2-benzyl-2-dimethylamino-l- (morpholinophenyl) - butanone-1 as active component) , acylphosphines such as for instance Lucerine TPO (TM) (2 , 4, 6-trimethylbenzoyl- diphenyl-phosphine-oxide) .
  • TM Lucerine TPO
  • TM 2, 4, 6-trimethylbenzoyl- diphenyl-phosphine-oxid
  • the invention also relates to the cured resin composition, obtained with the resin composition according to the invention , as well as to objects manufactured from the cured resin composition.
  • the polymerisation reactions were monitored by means of the Photo-DSC (Differential Scanning
  • the polymerisation reactions were monitored by means of the Real Time - Fourier Transform Infra Red (RT-FTIR) technique.
  • RT-FTIR Real Time - Fourier Transform Infra Red
  • One of the main differences of this technique and the Photo-DSC technique is that the light dose has a much higher intensity (about 500 mW/cm 2 ) . Therefore, the time scale of curing is one of seconds instead of minutes, as is the case with Photo- DSC.
  • Use was made of a Bruker IFSS 55 RT-FTIR equipped with an Oriel system fitted with a 200 W Hg-lamp. All experiments were performed under nitrogen, unless otherwise stated.
  • Example I nitrile-terminated polypropylene imine dendrimer
  • Example I was repeated with 20 mg(l wt.%) of the nitrile-terminated polypropylene imine dendrimers DAB (ACN) 8 and DAB (ACN) 16 (generations 1.5 and 2.5) .
  • the results are presented in Table 1.
  • the dendrimers DAB (ACN) 4 , DAB (ACN) 8 and DAB (ACN) 16 yield a conversion that is superior to that according to Comparative Examples A and B while the curing rate is superior or comparable to that according to Comparative Examples A and B.
  • Example IV phenoxyethylacrylate-terminated polypropylene imine dendrimer
  • Example IV was repeated with 20 mg (1 wt.%) of the amino-terminated polypropylene imine dendrimers DAB(PA) 8 , DAB(PA) 16 , DAB(PA) 32 and DAB(PA) 64 (DSM Astramol ® , generations 2, 3, 4 and 5) .
  • the results are presented in Table 2. All modified dendrimers that were tested give a conversion that is higher than the conversion achieved according to Comparative Examples A and B. All dendrimers also give a curing rate that is superior or comparable to that according to Comparative Examples A and B. 17
  • DAB (acrylate) x reaction product of DAB(PA) X and phenoxyethyl acrylate.
  • Example I was repeated with varying amounts of amine (0.1 to 10%). The results are presented in Table 3. They show that at an approximately constant and high conversion a curing rate can be achieved that increases with the amount of amine. - 18 -
  • dendrimers were obtained from DSM N.V. (Heerlen, the Netherlands) .
  • Table 4 Conversions and curing rates for different amines, determined using RT-FTIR.
  • compositions according to the invention show the highest curing rate and the highest conversion after 10 seconds of irradiation in comparison to the compositions according to the state of the art (dimethylethanol amine).
  • a set of films were made, consisting of 96 weight% Ebercryl 80, 2 weigth% benzophenone and 2 weight% amino-terminated polypropylene imine dendrimer.
  • the films were cured with a Fusion F600 D-lamp (Fusion Systems Inc.) with a 1 J/cm 2 total dose (UV-A, UV-B and UV-C) .
  • UV-A, UV-B and UV-C 1 J/cm 2 total dose

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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)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Cette invention se rapporte à une composition de résine susceptible de durcir par exposition à un rayonnement, qui comporte au moins une résine susceptible de durcir par exposition à un rayonnement, un composé photo-excitable et une amine aliphatique, ladite amine étant un composé possédant au moins un groupe amine tertiaire, ce groupe amine tertiaire pouvant être remplacé par au moins un substituant qui est une chaîne aliphatique contenant au moins un groupe extracteur d'électrons. Il est possible de polymériser cette composition de résine et d'atteindre un degré de conversion supérieur à celui obtenu par des procédés conformes à l'état antérieur de la technique. En outre, cette composition de résine peut être polymérisée à une vitesse de polymérisation accélérée, qui dépasse ou au minimum égale la vitesse de polymérisation d'une telle composition de résine conformément à l'état antérieur de la technique. De préférence, l'amine est un dendrimère ramifié ou en forme d'étoile qui contient au moins un groupe amine tertiaire et dans lequel un groupe extracteur d'électrons est lié par l'intermédiaire d'une chaîne alkyle à l'atome d'azote du groupe amine tertiaire. Les dendrimères de nitrile et de polypropylène imine à terminaisons ester constituent des dendrimères adaptés.
EP98937870A 1997-08-11 1998-07-30 Composition a base de resine, a durcissement ameliore par exposition a un rayonnement Withdrawn EP1003789A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL1006761A NL1006761C2 (nl) 1997-08-11 1997-08-11 Harssamenstelling met een verbeterde stralingsuithardbaarheid.
NL1006761 1997-08-11
PCT/NL1998/000439 WO1999007746A1 (fr) 1997-08-11 1998-07-30 Composition a base de resine, a durcissement ameliore par exposition a un rayonnement

Publications (1)

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EP1003789A1 true EP1003789A1 (fr) 2000-05-31

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EP98937870A Withdrawn EP1003789A1 (fr) 1997-08-11 1998-07-30 Composition a base de resine, a durcissement ameliore par exposition a un rayonnement

Country Status (9)

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EP (1) EP1003789A1 (fr)
JP (1) JP2001512751A (fr)
KR (1) KR20010022660A (fr)
CN (1) CN1274364A (fr)
AU (1) AU8651398A (fr)
BR (1) BR9811894A (fr)
CA (1) CA2300301A1 (fr)
NL (1) NL1006761C2 (fr)
WO (1) WO1999007746A1 (fr)

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Publication number Priority date Publication date Assignee Title
SE520406C2 (sv) * 2000-09-13 2003-07-08 Perstorp Specialty Chem Ab Strålningshärdbar dendritisk oligomer eller polymer
US7538144B2 (en) 2004-07-15 2009-05-26 Agfa Graphics, N.V. Photoreactive polymers
DE602004008602T2 (de) * 2004-07-15 2008-06-12 Agfa Graphics N.V. Neue strahlenhärtbare Zusammensetzungen
US7507785B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Polymeric co-initiators
EP1616897B1 (fr) * 2004-07-15 2010-03-31 Agfa Graphics N.V. Nouveaux co-initiateurs polymeriques
US7396861B2 (en) 2004-07-15 2008-07-08 Agfa Graphics Nv Radiation curable compositions
US7507773B2 (en) 2004-07-15 2009-03-24 Agfa Graphics N.V. Radiation curable compositions
CN101573387B (zh) 2006-12-21 2013-05-29 爱克发印艺公司 可辐射固化组合物
IN2009CN03580A (fr) 2006-12-21 2015-09-11 Agfa Graphics Nv
EP3243857A1 (fr) * 2016-05-13 2017-11-15 Centre National de la Recherche Scientifique - CNRS - Polyuréthanes à séquence définie uniforme et leurs utilisations en tant qu'étiquettes moléculaires

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DE3029276A1 (de) * 1980-08-01 1982-02-18 Etablissement Dentaire Ivoclar, Schaan Photopolymerisierbare masse, insbesondere fuer dentalzwecke

Non-Patent Citations (1)

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Title
See references of WO9907746A1 *

Also Published As

Publication number Publication date
CN1274364A (zh) 2000-11-22
WO1999007746A1 (fr) 1999-02-18
JP2001512751A (ja) 2001-08-28
CA2300301A1 (fr) 1999-02-18
KR20010022660A (ko) 2001-03-26
NL1006761C2 (nl) 1999-02-12
BR9811894A (pt) 2000-08-22
AU8651398A (en) 1999-03-01

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