WO1997000276A1 - Compositions de resine durcissables par rayons energetiques actifs, article durci et lentille optique obtenue a partir de celui-ci, et nouveaux (meth)acrylates correspondants - Google Patents

Compositions de resine durcissables par rayons energetiques actifs, article durci et lentille optique obtenue a partir de celui-ci, et nouveaux (meth)acrylates correspondants Download PDF

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Publication number
WO1997000276A1
WO1997000276A1 PCT/BE1996/000062 BE9600062W WO9700276A1 WO 1997000276 A1 WO1997000276 A1 WO 1997000276A1 BE 9600062 W BE9600062 W BE 9600062W WO 9700276 A1 WO9700276 A1 WO 9700276A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
active energy
energy ray
curable resin
Prior art date
Application number
PCT/BE1996/000062
Other languages
English (en)
Inventor
Michio Kochi
Original Assignee
Ucb, S.A.
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 JP17132195A external-priority patent/JPH08337621A/ja
Priority claimed from JP8715896A external-priority patent/JPH09249719A/ja
Priority claimed from JP14217696A external-priority patent/JPH0959535A/ja
Application filed by Ucb, S.A. filed Critical Ucb, S.A.
Priority to EP96917296A priority Critical patent/EP0832144A1/fr
Publication of WO1997000276A1 publication Critical patent/WO1997000276A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
    • C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to active energy ray-curable resin compositions which can be cured by an active energy ray such as an ultraviolet ray or electron beam and, further the present invention relates to a cured article therefrom having a high refractive index, a Fresnel lens or lenticular lens wherein a thermoplastic resin plate is combined with a layer of the cured article, and a transmission type screen in which a thermoplastic resin is combined with two-layers of the cured article.
  • an active energy ray such as an ultraviolet ray or electron beam
  • a cured article therefrom having a high refractive index, a Fresnel lens or lenticular lens wherein a thermoplastic resin plate is combined with a layer of the cured article, and a transmission type screen in which a thermoplastic resin is combined with two-layers of the cured article.
  • the active energy ray-curable resin compositions are excellent in workability for forming, in properties of a coating layer, and from an economical viewpoint.
  • the active energy ray-curable resin compositions can provide a cured article having a high refractive index, and an optical lens wherein a thermoplastic resin is combined with two-layers of the cured article.
  • the invention also relates to novel (meth)acrylates usable in some of these compositions.
  • An active energy ray-curable resin composition which can be cured by irradiation of an active energy ray such as ultraviolet ray or electron beam has been widely used in a variety of fields such as printing fields, coatings fields, and electric fields, etc., because of its excellent productivity and low pollution from a viewpoint of recent environmental problems.
  • active energy ray-curable resin compositions have advantageous properties which are (1) a solvent free and low pollution type, (2) capability of high speed curability and high productivity of products, (3) capability of slight shrinkage in volume because of curing by solid of 100%, and (4) capability of slight thermal loss and minor adverse thermal affection to base materials, etc.
  • the active energy ray-curable resin compositions there may be cited resin for inks, coating for plastics, coating for films, coating for metals, coating for furniture, lining materials, adhesives, insulating varnishes for electronics, insulating sheet, laminated sheet, printed circuit board, resist ink, and encapsulating materials for semiconductors.
  • the active energy ray-curable resin compositions have been employed as resins for moulding and as a cured article having a high refractive index, such as coatings for an optical lens, particularly, a Fresnel lens or a lenticular lens, and a transmission type screen in which a Fresnel lens is combined with a lenticular lens, owing to the above-described advantageous properties.
  • a Fresnel lens or a lenticular lens requires thin thickness, and further a high refractive index, for example, more than 1.47, preferably more than 1.50.
  • the preparation of a cured article for a Fresnel lens or a lenticular lens requires quick curing rate by active energy, and the cured article must have an excellent scratch resistance and a moderate flexibility for giving an excellent recovery property in a dent generated by compression.
  • resins for moulding having a high refractive index in a cured article for example, there are disclosed compounds containing sulphur in JP-A-5255464 and JP-B-94025232, and there are disclosed compounds containing halogens such as bromine except fluorine in JP-A-5117348, there are disclosed compounds having bromine in JP-A-4216814, and further there are disclosed acrylate monomer having peculiar aromatic rings in JP-A- 5065318.
  • the compounds disclosed in these JP's are peculiar, and articles moulded from these compounds are not sufficient in scratch resistance and recovery property in a dent generated by compression.
  • the present inventor has found active energy ray-curable resin compositions capable of providing a cured article having a high refractive index, a high scratch resistance and an excellent recovery property in a dent generated by compression.
  • an active energy ray-curable resin composition based on a urethane(meth)acrylate comprising the reaction product of:
  • R- j _ is a hydrogen atom or a methyl group
  • R2 is independently a hydrogen or an alkyl group having a carbon number ranging from 1 to 10
  • R3, R 4 and R5 is independently a hydrogen, an alkyl group having a carbon number ranging from 1 to 10, and phenyl group or bromine
  • nl is an integer ranging from 1 to 7
  • n2 is an integer ranging from 0 to 20
  • Ra and Rb are independently a hydrogen or a methyl group
  • n3 is independently an integer ranging from 0 to 10
  • n4 is 0 or 1
  • n5 is an integer ranging from 0 to 5.
  • organic isocyanate having at least two isocyanate groups which are capable of reacting with a hydroxyl group there are specifically exemplified isocyanates such as tolylene diisocyanate, 4,4-diphenylme hane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylenebis(4-cyclohexylisocyanate) , 1,6-hexamethylene diisocyanate, isocyanurates such as trimer of hexamethylene diisocyanate and trimer of isophorone diisocyanate.
  • the organic isocyanates may be employed solely or in combination.
  • polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol
  • lactone- odified polyester polyols such as a polycaprolactone polyol and a butyrolactone polyol
  • polycarbonate polyols such as polycarbonate polyols.
  • the polyols may be employed solely or in combination. If the polyol which has at least two hydroxyl groups in the molecule has a molecular weight of less than 300, there is an unpractically decrease in flexibility of a cured article prepared from the active energy ray- curable resin composition of the present invention.
  • the compounds represented by general formulae (1) to (5) can be prepared by the reaction of acrylic acid, methacrylic acid, or a lactone- ' adduct thereof with an epoxy compound having at least one aromatic ring.
  • the reaction is carried out in a ratio of chemical equivalent of carboxylic *35 group ranging from 0.8 to 1.2, preferably from 0.9 to 1.1, with respect to 1 chemical equivalent of an epoxy group, and at a temperature range of 60 to 150°C, preferably from 80 to 120°C Catalysts are preferably employed in order to accelerate the reaction.
  • Catalysts are preferably employed in order to accelerate the reaction.
  • the catalysts there are specifically exemplified benzylmethylamine, triethylamine, and benzyl-trimethylammonium chloride, etc.
  • the catalysts are employed in an amount ranging from 0.1 to 10% by weight, and preferably from 0.3 to 5% by weight.
  • nl depends upon the lactone compound to be optionally employed, and n2 is the number of mole of the lactone compound to be introduced.
  • epsilon-caprolactone is employed as the lactone compound
  • both of Ra and Rb are a hydrogen
  • nl is 5.
  • the urethane(meth)acrylate is prepared by reaction of the components (a) , (b) , and (c) . More specifically, 1 equivalent of hydroxyl group in the component (b) is first allowed to react with from about 1.1 to 2.2 equivalent of isocyanate group in the component (a) at ordinary pressure and a temperature ranging from 60 to 90°C to prepare a urethane prepolymer. Subsequently, 1 equivalent of isocyanate group in the urethane prepolymer is allowed to react with from about 1.0 to 1.5, preferably from 1.0 to 1.2 equivalent of hydroxyl group in the component (c) at ordinary pressure and a temperature ranging from 60 to 90°C.
  • the catalysts there are specifically exemplified dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin disulphide, dibutyltin dibutoxide, etc.
  • the catalysts are employed in an amount ranging from 50 to 5000 ppm, and preferably from 250 to 1000 ppm.
  • the compound represented by general formula (6) it may be specifically exemplified a reaction product of modified-bisphenol type compounds such as an ethylene oxide-adduct of bisphenol A or a propylene oxide-adduct of bisphenol A with acrylic acid or methacrylic acid.
  • modified-bisphenol type compounds such as an ethylene oxide-adduct of bisphenol A or a propylene oxide-adduct of bisphenol A with acrylic acid or methacrylic acid.
  • the mark * represents saturation or unsaturation in the ring
  • R ⁇ is independently a hydrogen or a lower alkyl group
  • R2 is independently a hydrogen or a methyl group
  • n is an integer ranging from 1 to 10 which depends upon the amount by mole of ethylene oxide or propylene oxide to be introduced.
  • the reaction of the modified-bisphenol A type compounds with acrylic acid or methacrylic acid is carried out in a chemical equivalent ratio ranging from 0.8 to 1.2, preferably from 0.9 to 1.1 of acrylic acid or methacrylic acid with respect to 1 chemical equivalent of hydroxyl group in the modified bisphenol A type compounds, and at a temperature range of 60 to 150, preferably from 80 to 120°C.
  • Usual catalysts are preferably employed in order to accelerate the reaction.
  • the compound represented by general formula (6) can be employed in an amount ranging from 5 to 60 parts by weight based on 100 parts by weight of the urethane(meth)acrylate.
  • the active energy ray-curable resin composition of the present invention there can be mixed 1 to 10 parts by weight of a photo- polymerization initiator based on 100 parts by weight of the urethane(meth)acrylate.
  • photo-polymerization initiator specific examples are benzoin, benzoin methylether, benzoin isopropylether, acetophenone, 2,2-dimethoxy-2- phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-l-[4- (methylthio)phenyl] -2-morpholino-propane-l-on, 2-hydroxydi-2-methyl-1- phenylpropane-1-on, N,N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2- amylanthraquinone, 2-aminoanthraquinone, 2,4-diethylthioxanthone, 2,4- diisoprop
  • an accelerator such as ethylester of N,N-dimethylaminobenzoic acid, triethanolamine, and triethylamine, etc.
  • the photo-polymerization initiators and accelerators may be employed solely or in combination.
  • the photo-polymerization initiator may be employed in an amount ranging from 1 to 10 parts by weight, preferably from 3 to 6 parts by weight based on 100 parts by weight of the above-mentioned urethane(meth)acrylate.
  • an ethylenically unsaturated monomer other than the compounds represented by the formulae (1) to (5) in order to adjust the viscosity of the composition or to improve the properties in coating layers.
  • the ethylenically unsaturated monomers examples are styrene,
  • (meth)acrylonitrile ethyl(meth)acrylate, butyl(meth)acrylate, 2- ethtylhexyl(meth)acrylate, isobornyl (meth)acrylate, cyclohexyl(meth)acrylate, 2-chlorostyrene, phenoxyethyl(meth)acrylate, (meth)acrylic acid, 2-hydroxyethyl(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate, etc.
  • These ethylenically unsaturated monomers may be employed solely or in combination.
  • the urethane(meth)acrylate to be employed in the present invention can be prepared by conventional reaction methods.
  • the above-described organic isocyanate having at least two isocyanate groups is allowed to react with a polyol having a molecular weight of at least 300 which has at least two hydroxyl groups in the molecule, and compounds represented by the general formulae (1) to (5) at a temperature ranging from 60 to 90°C under ordinary pressure.
  • Catalysts are preferably employed in order to accelerate the reaction.
  • the catalysts there are specifically exemplified 5 dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulphide, and , dibutyltin dibuthoxide, etc.
  • the catalysts are employed in an amount ranging from 50 to 5000 ppm, and preferably from 250 to 1000 ppm.
  • the reaction is terminated when a fixed concentration of residual isocyanate groups is reached. 10
  • a cured article having a refractive index of not less than 1.47 at 25°C moulded from the active energy ray-curable resin composition.
  • the cured article having a refractive index of not less than 1.47 at 25°C can be moulded from the active energy ray-curable resin composition of 15 the first aspect of the present invention described hereinabove.
  • Refractive index is preferably more than 1.50 at 25°C. Refractive index can be adjusted by controlling the combination of essential and optional components to be employed in the urethane(meth)acrylates.
  • Additivity rule based on components can be applied in refractive 20 index of the cured article as described below.
  • Refractive index of a mixture (the sum of respective refractive index x respective weight % in starting materials) /100.
  • the cured article of the present invention has not only a high refractive index but also a capability of forming flexible coating layers. Accordingly, a recovery property in a dent generated by compression is sufficient even though hands of workers or other parts are in contact with the surface when being stored and transported.
  • the cured article can be prepared by irradiating the active energy ray-curable resin composition of the present invention with ultraviolet ray or electron beam. ' Irradiation by ultraviolet ray is carried out with a mercury lamp or metal halide lamp, etc. from which curing energy of 100 to 1000 mJ/cm 2 is * 35 preferably radiated.
  • irradiation by electron beam is preferably carried out at the conditions of voltage for pressurization of 150 to 250 KeV and irradiation quantity of 1 to 5 mega-rad. Irradiation is generally carried out in a resin-made mould.
  • a Fresnel lens or lenticular lens wherein a thermoplastic resin having a Haze value of below 10% is combined with a layer of the cured article in the second aspect.
  • a transmission type screen wherein a thermoplastic resin having a Haze value of below 10% is combined with two layers of the cured article in the second aspect.
  • Optical lens particularly, a Fresnel lens, a lenticular lens, and a transmission- ype screen combined thereof can be prepared by the combination of a cured article prepared from the active energy ray-curable resin composition of the present invention with a thermoplastic resin having a Haze value of not more than 10% based on JIS K7105.
  • a Fresnel lens can be prepared by the following steps. First of all, the active energy ray-curable resin composition of the present invention is coated inside a mould for a Fresnel lens on which concentrically circular grooves are formed to prepare a coating layer having the thickness of 100 to 500 microns. Subsequently, onto the coating layer, there is stuck a plate having 50 microns to 3 mm prepared from a thermoplastic resin plate having a Haze value of not more than 10%.
  • thermoplastic resin plate through the coating layer, irradiation is carried out to cure the coating layer, for example, with a high pressure mercury lamp from which ultraviolet ray of 400 mJ/cm 2 is radiated. Subsequently, a Fresnel lens having the thiclcness of 150 microns to cure the coating layer, for example, with a high pressure mercury lamp from which ultraviolet ray of 400 mJ/cm 2 is radiated. Subsequently, a Fresnel lens having the thiclcness of 150 microns to
  • 3.5 mm can be prepared by removing the mould for Fresnel lens.
  • a lenticular lens can be also prepared with a mould for a lenticular lens similarly to the above descriptions.
  • the active energy ray-curable resin composition of the present invention is coated inside a mould for a lenticular lens on which minor semicylindrical projections are formed to prepare a coating layer having the thickness of 100 to 500 microns. Subsequently, from the thermoplastic resin plate side, irradiation is carried out to cure the coating layer, for example, with a high pressure mercury lamp from which ultraviolet ray of 400 mJ/cm 2 is radiated.
  • a transmission-type screen combined thereof can be by the following steps. First of all, a Fresnel lens or a lenticular lens can be prepared as described hereinabove. Subsequently, thermoplastic resin plate in the Fresnel lens or lenticular lens is stuck on coating layer coated inside a mould for a lenticular lens or a Fresnel lens. Subsequently, irradiation is carried out to cure the coating layer. As a result, a transmission-type screen can be prepared by removing the mould for a lenticular lens or a 5 Fresnel lens .
  • thermoplastic resin having a Haze value of not more than 10% based on JIS K7105 there are specifically exemplified a polymethylmethacrylate, a polystyrene, a polycarbonate, and a copolymer thereof. Of those, a polymethylmethacrylate and a polystyrene are 10 preferably employed.
  • an active energy ray-curable resin composition containing per 100 parts by weight of the combined weights of (d) , (e) , and (f) :
  • organic polyisocyanate having at least one aromatic ring or at least one alicyclic ring there are specifically exemplified isocyanates such as tolylene diisocyanate, 4, 4-diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, methylenebis (4- 25 cyclohexylisocyanate) , isocyanurates such as a trimer of hexamethylene diisocyanate and a trimer of isophorone diisocyanate.
  • the organic isocyanates may be employed solely or in combination.
  • the urethane(meth)acrylate which is the component (d) can be prepared by a reaction of the above-described organic polyisocyanate with a 30 (meth)acrylate having a hydroxyl group.
  • the (meth)acrylate having a hydroxyl group there are specifically exemplified 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth) crylate, 2- ' hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4- hydroxybutyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, an ethylene '35 oxide-modified phthalic (meth)acrylate, a propylene oxide-modified phthalic(meth)acrylate, a polyethyleneglycol mono(meth)acrylate, pentaerythritol di (meth)acrylate, pentaerythritol tri (meth)acrylate, and a lactone-modified 2-hydroxyethyl (meth)acrylate.
  • the (meth) crylates having a hydroxyl group may be employed solely or in combination.
  • polyols are additionally employed.
  • the polyols there are specifically exemplified a polyethyleneglycol, a polypropyleneglycol, a polytetramethylene glycol, and a polylactone polyol, etc.
  • the polyols may be employed solely or in combination.
  • the reaction can be carried out by conventional processes. Specifically, at least one of the polyisocyanates, at least one of the (meth)acrylates having a hydroxyl group, and optionally at least one of the polyols, are allowed to react at ordinary pressures and at a temperature ranging from 60 to 90°C.
  • catalysts such as dibutyltin dilaurate, dibutyltin diethylhexoate, and dibutyltin sulphide, etc.
  • the catalysts are employed in an amount ranging from 50 to 5000 ppm, and preferably from 250 to 1000 ppm.
  • the active energy ray-curable resin composition of the fifth aspect in the present invention can be prepared by mixing 15 to 95% by weight, preferably from 30 to 80% by weight of the urethane(meth)acrylate which is the component (d) with 1 to 8% by weight, preferably from 3 to 6% of a (meth) crylic-based monomer having at least one bromine atom which is the component (e) , and a curable monomer which is the component (f) .
  • the toughness of the cured layer unpreferably decreases and, contrarily, in the case when it exceeds 90% by weight, there is unpreferably an increase of the viscosity of the active energy ray-curable resin composition, resulting in that the composition is not appropriate for practical uses.
  • the refractive index does not increase and, contrarily, in the case when it exceeds 8%, not only the scratch resistance and recovery property decrease, but also the cost of the composition disadvantageously increases.
  • the (meth)acrylate monomer having at least one bromine atom there is employed at least one compound selected from the group consisting of a methyl (meth)acrylate-2,4, 6-tribromophenol, a brominated di(meth)acrylate of an ethyleneoxide adduct of bisphenol A, and compounds represented by general formulae (7) to (9) (7)
  • R ] _ is a hydrogen atom or a methyl group
  • R 2 is independently a hydrogen or an alkyl group having a carbon number ranging from 1 to 10
  • R3 , R4, and R is independently a hydrogen, an alkyl group having a carbon number ranging from 1 to 10, and phenyl group or bromine in which at least one of R T , R4, and R5 is a bromine
  • nl is an integer ranging from 1 to 7
  • n2 is an integer ranging from 0 to 20
  • Ra and Rb are independently a hydrogen or a methyl group
  • n3 is independently an integer ranging from 0 to 10.
  • the compounds represented by the above- described general formulae (7) to (9) essentially includes at least one of bromine atom compared to the compounds represented by the above-described general formulae (1) to (3) in the first aspect in which bromine atom is not essential.
  • Compounds (7) to (9) are prepared in the same way as compounds (1) to (3).
  • a curable monomer which is the component (f) is optionally employed in order to adjust the viscosity of the composition and/or the properties of coating layers.
  • curable monomer there are specifically exemplified styrene, (meth)acrylonitrile, ethyl(meth)acrylate, butyl(meth)acrylate, 2- ethylhexyl(meth)acrylate, isobornyl(meth)acrylate, cyclohexyl(meth)acrylate, 2-chlorostyrene, phenoxyethyl(meth)acrylate, acrylic acid, (meth)acrylic acid, 2-hydroxyethyl(meth)acrylate, 1,6- hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, and dipentaerythritol hexa(meth)acrylate, etc.
  • the compound represented by the above-described general formula (6) is preferably added to the composition in order to improve the mechanical strength of a cured article as well as the active energy ray- curable resin composition in the first aspect.
  • the compound represented by the general formula (6) can be employed in an amount ranging from 5 to 60% by weight based on 100 parts by weight of the components (d) , (e) , and (f) .
  • the active energy ray-curable resin composition of the fifth aspect it may be added from 0.5 to 15 parts by weight, preferably from 3 to 8 parts by weight of the photo-polymerization initiator and accelerator described in the first aspect, based on 100 parts by weight of the components (d) , (e) , and (f) .
  • a cured article having a refractive index of not less than 1.47 at 25 3 C moulded from the active energy ray-curable resin composition in the fifth aspect.
  • the cured article can be prepared as well as in the second aspect.
  • a Fresnel lens or lenticular lens wherein a thermoplastic resin having a Haze value of below 10% is combined with a layer of the cured article as in the sixth aspect.
  • the Fresnel lens or lenticular lens can be prepared as well as in the third aspec .
  • a transmission type screen wherein a thermoplastic resin having Haze value of below 10% is combined with two layers of the cured article as in the sixth aspect. 5
  • the transmission type screen can be prepared as well as in the fourth aspect.
  • an active energy ray-curable resin composition containing:
  • ] _ is independently a hydrogen or a lower alkyl group
  • R 2 is independently a hydrogen or a methyl group
  • n is an integer ranging from 1 to 10.
  • the component (d) in the ninth aspect is identical to the component 20 (d) in the fifth aspect, and the component (f) in the ninth aspect is identical to the component (f) in the fifth aspect.
  • the compound represented by the above-described general formula (6) is preferably added to the composition in order to improve the
  • the compound represented by the general formula (6) can be employed in an amount ranging
  • the active energy ray-curable resin composition of the ninth aspect it may be added from 0.5 to 15 parts by weight, preferably from 3 to 8 parts by weight of the photo-polymerization initiator and accelerator described in the first and fifth aspects, based on 100 parts by weight of the components (d) and (f) .
  • a cured article having a refractive index of not less than 1.47 at 25°C moulded from the active energy ray-curable resin composition in the ninth aspect.
  • the cured article can be prepared as well as in the second and sixth aspects.
  • a Fresnel lens or lenticular lens wherein a thermoplastic resin having a Haze value of below 10% is combined with a layer of the cured article in the ninth aspect.
  • the Fresnel lens or lenticular lens can be prepared as well as in the third and seventh aspects.
  • thermoplastic resin having Haze value of below 10% is combined with two layers of the cured article in the ninth aspect.
  • the transmission type screen can be prepared as well as in the fourth and eighth aspect.
  • new (meth)acrylates corresponding to the compounds of formulae (3) and (5) of the first aspect of the invention. More specifically, 3- hydroxy-4-benzoate cyclohexylmethyl methacrylate, synthesised in following Synthesis Example 3 and used to prepare the urethanemethacrylate UA-8 of Synthesis Example 8, is a new compound responding to formula (3) . Also, 2- hydroxy-2,4-diphenyl-4-methyl-pentylacrylate synthesised in following Synthesis Example 4 and used to prepare the urethaneacrylate UA-9 in Synthesis Example 9, is a new compound responding to formula (5) .
  • a coating layer having the thickness of 200 microns was coated on a glass plate. Subsequently, the coating layer was irradiated twice by an ultraviolet ray with a power of 120W/cm and a velocity of 5m/min with a high pressure mercury lamp to prepare a cured layer. Subsequently, the cured coating layer was peeled from the glass plate. UV curability was evaluated by finger-touch. Evaluation grade is as follows.
  • Refractive index of the cured coating layer was measured with an Abbe refractometer at 25°C according to JIS K0062.
  • the cured coating layer was pushed at the pressure of 30 kg/cm 2 with a metal rod having the diameter of 5 mm at the point for 5 seconds, and the time after which a dent disappears was measured.
  • a reaction vessel equipped with an agitator, a thermometer, a dropwise funnel, and an inlet for supplying dried air was placed in an oil bath, and charged with 240g (2 mole) of styrene oxide (manufactured by Daicel Chemical Industries, Ltd.) and 0.5g of triethylamine; the vessel was then heated to 90°C.
  • Synthesis Example 4 A warm water-jacketed reaction vessel equipped with an agitator, a thermometer, a dropwise funnel, and an inlet for supplying nitrogen gas was charged with 472g (2.2 mole) of 2,4-diphenyl-4-methyl-l-pentene; the vessel was then heated to 50 C C.
  • Synthesis Example 5 A reaction vessel equipped with an agitator, a thermometer, a dropwise funnel, and an inlet for supplying dried air was placed in an oil bath, and charged with 444g (2 mole) of isophorone diisocyanate and 0.5g of dibutyltin dilaurate; the vessel was then heated to 70°C. Subsequently, 53Og (1 mole) of a polycaprolactone diol having a molecular weight of 530 (Placcel 205 manufactured by Daicel Chemical Industries, Ltd.) was gradually added from the dropwise funnel. After the completion of addition, the reaction was allowed to continue until the concentration of residual isocyanate groups attained a theoretical value.
  • the polycarbonate diol (CD-205) has a chemical formula of HO- (CH 2 ) 6 -[-0C0(CH 2 )0-] n -H.
  • Resin compositions were prepared according to respective mixing ratio (parts by weight) as shown in Tables 1 and 2, and the properties of coating layers cured by ultraviolet ray were evaluated. Results are shown in Tables 1 and 2.
  • Table 2 Table 2
  • EOMDA an ethylene oxide-modified bisphenol type diacrylate
  • IBOA-B isobornyl acrylate which is IBOA-B manufactured by
  • PEA phenoxyethyl acrylate
  • DPEHA dipentaerythritol hexaacrylate
  • MATBP l-methylacrylate-2, 4, 6-tribromophenol
  • DC-1173 2-hydroxy-2-meth-l-phenylpropane-l-on which is Darocure
  • a reaction vessel equipped with an agitator, a thermometer, a dropwise funnel, and an inlet for supplying dried air was placed in an oil bath, and charged with 348g (2 mole) of 2,4-tolylene diisocyanate and 0.5g of dibutyltin dilaurate, and the vessel was then heated to 70°C. Subsequently, 688g (2 mole) of an epsilon-caprolactone-modified 2- hydroxyethyl acrylate having a molecular weight of 344 (PCL FA-2 manufactured by Daicel Chemical Industries, Ltd.) was added dropwise from the dropwise funnel.
  • PCL FA-2 manufactured by Daicel Chemical Industries, Ltd.
  • Resin compositions were prepared according to respective mixing ratio (parts by weight) as shown in Table 3. The properties of coating layers cured by an ultraviolet ray were then evaluated. Results are shown in Table 3.
  • MBPADA a modified bisphenol type diacrylate which is one of the compounds represented by the general formula (6) .
  • IC 184 1-hydroxycyclohexyl phenylketone which is Irugacure 184 manufactured by Ciba-Geigy, AG.
  • IBOA-B isobornyl acrylate manufactured by Daicel-UCB, Ltd.
  • MBPADA an ethylene oxide-modified bisphenol type diacrylate which is

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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)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Compositions de résine durcissables par rayons énergétiques actifs, et nouveaux (méth)acrylates. Ces compositions de résine durcissables par rayons énergétiques actifs présentent une stabilité et une aptitude au durcissement et au revêtement excellentes par rapport aux compositions de résine classiques durcissables par rayons énergétiques actifs. Les articles durcis préparés à partir desdites compositions de résine durcissables par rayons énergétiques actifs présentent un indice de réfraction élevé, une excellente résistance à la rayure, et une souplesse moyenne qui leur confère une excellente caractéristique de recouvrance en cas de déformation due à la compression, et ces articles sont utilisables de préférence comme lentille optique du type lentille de Fresnel ou lentille lenticulaire.
PCT/BE1996/000062 1995-06-14 1996-06-14 Compositions de resine durcissables par rayons energetiques actifs, article durci et lentille optique obtenue a partir de celui-ci, et nouveaux (meth)acrylates correspondants WO1997000276A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96917296A EP0832144A1 (fr) 1995-06-14 1996-06-14 Compositions de resine durcissables par rayons energetiques actifs, article durci et lentille optique obtenue a partir de celui-ci, et nouveaux (meth)acrylates correspondants

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP17132295 1995-06-14
JP17132195A JPH08337621A (ja) 1995-06-14 1995-06-14 活性エネルギー線硬化型樹脂組成物
JP7/171321 1995-06-14
JP7/171322 1995-06-14
JP8715896A JPH09249719A (ja) 1996-03-15 1996-03-15 活性エネルギー線硬化型組成物およびその硬化物
JP8/87158 1996-03-15
JP14217696A JPH0959535A (ja) 1995-06-14 1996-05-13 活性エネルギー線硬化型樹脂組成物、その硬化物およびフレネルレンズ
JP8/142176 1996-05-13

Publications (1)

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WO1997000276A1 true WO1997000276A1 (fr) 1997-01-03

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EP (1) EP0832144A1 (fr)
CA (1) CA2222213A1 (fr)
WO (1) WO1997000276A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000075211A1 (fr) * 1999-06-03 2000-12-14 Dsm N.V. Composition de resine photodurcissable et elements optiques
WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique
US6852773B2 (en) 2000-01-14 2005-02-08 Dsm Ip Assets B.V. Photocurable resin composition and optical parts
US7173072B2 (en) 2003-05-08 2007-02-06 Jsr Corporation Radiation-curable resin composition for forming optical part and optical part
WO2008031601A1 (fr) * 2006-09-13 2008-03-20 Dsm Ip Assets B.V. Revêtement hydrophile antimicrobien comprenant des particules d'argent métallique
US8258201B2 (en) * 2008-05-29 2012-09-04 Asahi Glass Company, Limited Photocurable composition and process for producing molded product having fine pattern on its surface
CN111349196A (zh) * 2018-12-21 2020-06-30 义获嘉伟瓦登特公司 用于通过立体光刻制备具有断裂韧性的牙科部件的组合物
US11697696B2 (en) 2018-12-21 2023-07-11 Ivoclar Vivadent Ag Compositions for the production of transparent dental parts by means of stereolithography

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USRE29131E (en) * 1970-09-02 1977-02-01 Union Carbide Corporation Radiation-curable acrylate-capped polycaprolactone compositions
US4487904A (en) * 1983-09-21 1984-12-11 Toray Industries, Inc. Urethanized acrylic resin material for plastic lens and lens composed thereof
JPH05117348A (ja) * 1991-10-31 1993-05-14 Dainippon Printing Co Ltd フレネルレンズ用紫外線硬化型樹脂組成物及び透過型スクリーン
EP0606905A2 (fr) * 1993-01-14 1994-07-20 Daiso Co., Ltd. Compositions polymérisables et lentilles en matière platique ayant un indice de réfraction élevé

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USRE29131E (en) * 1970-09-02 1977-02-01 Union Carbide Corporation Radiation-curable acrylate-capped polycaprolactone compositions
US4487904A (en) * 1983-09-21 1984-12-11 Toray Industries, Inc. Urethanized acrylic resin material for plastic lens and lens composed thereof
JPH05117348A (ja) * 1991-10-31 1993-05-14 Dainippon Printing Co Ltd フレネルレンズ用紫外線硬化型樹脂組成物及び透過型スクリーン
EP0606905A2 (fr) * 1993-01-14 1994-07-20 Daiso Co., Ltd. Compositions polymérisables et lentilles en matière platique ayant un indice de réfraction élevé

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DATABASE WPI Week 7303, Derwent World Patents Index; AN 03779U, XP002013761, "COLD SETTING COATING COMPOSITION" *
DATABASE WPI Week 9324, Derwent World Patents Index; AN 191540, XP002013762, "ULTRAVIOLET CURE RESIN COMPOSITION" *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000075211A1 (fr) * 1999-06-03 2000-12-14 Dsm N.V. Composition de resine photodurcissable et elements optiques
US6710097B2 (en) 1999-06-03 2004-03-23 Dsm N.V. Photocurable resin composition and optical parts
US6852773B2 (en) 2000-01-14 2005-02-08 Dsm Ip Assets B.V. Photocurable resin composition and optical parts
WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique
US7173072B2 (en) 2003-05-08 2007-02-06 Jsr Corporation Radiation-curable resin composition for forming optical part and optical part
WO2008031601A1 (fr) * 2006-09-13 2008-03-20 Dsm Ip Assets B.V. Revêtement hydrophile antimicrobien comprenant des particules d'argent métallique
US8258201B2 (en) * 2008-05-29 2012-09-04 Asahi Glass Company, Limited Photocurable composition and process for producing molded product having fine pattern on its surface
CN111349196A (zh) * 2018-12-21 2020-06-30 义获嘉伟瓦登特公司 用于通过立体光刻制备具有断裂韧性的牙科部件的组合物
US11697696B2 (en) 2018-12-21 2023-07-11 Ivoclar Vivadent Ag Compositions for the production of transparent dental parts by means of stereolithography
US11753537B2 (en) 2018-12-21 2023-09-12 Ivoclar Vivadent Ag Compositions for the production of fracture-tough dental parts by means of stereolithography

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CA2222213A1 (fr) 1997-01-03
EP0832144A1 (fr) 1998-04-01

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