WO2002029448A2 - Composition de resine photodurcissable et materiau optique - Google Patents

Composition de resine photodurcissable et materiau optique Download PDF

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Publication number
WO2002029448A2
WO2002029448A2 PCT/NL2001/000714 NL0100714W WO0229448A2 WO 2002029448 A2 WO2002029448 A2 WO 2002029448A2 NL 0100714 W NL0100714 W NL 0100714W WO 0229448 A2 WO0229448 A2 WO 0229448A2
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WO
WIPO (PCT)
Prior art keywords
acrylate
meth
resin composition
group
urethane
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PCT/NL2001/000714
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English (en)
Other versions
WO2002029448A3 (fr
Inventor
Takayoshi Tanabe
Masakatsu Ukon
Jiro Ueda
Takashi Ukachi
Original Assignee
Dsm N.V.
Jsr Corporation
Japan Fine Coatings Co., Ltd.
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Application filed by Dsm N.V., Jsr Corporation, Japan Fine Coatings Co., Ltd. filed Critical Dsm N.V.
Priority to AU2002211071A priority Critical patent/AU2002211071A1/en
Publication of WO2002029448A2 publication Critical patent/WO2002029448A2/fr
Publication of WO2002029448A3 publication Critical patent/WO2002029448A3/fr

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    • 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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

Definitions

  • the present invention relates to a photocurable resin composition. More particularly, the present invention relates to a photocurable resin composition useful for forming optical parts, for example, a prism lens sheet used for a backlight of a liquid crystal display and a Fresnel lens sheet or a lenticular lens sheet used for a screen of a projection TV or a backlight using such sheets.
  • Lenses such as a Fresnel lens and a lenticular lens have been manufactured by a press method or a cast method which require a long period of time for manufacturing. Therefore, productivity of there methods was poor.
  • a method of manufacturing a lens using a UV-curable resin has been attempted in recent years. Such a method comprises pouring a UV-curable resin composition between a mold having a lens shape and a transparent resin substrate and curing the composition by irradiating ultraviolet rays from the side of the substrate. This method ensures manufacture of a lens in a short period of time.
  • a UV-curable resin composition for a translucent screen which comprises (A) a urethane (meth)acrylate produced by reacting (a) a diol compound produced by reacting bisphenol A with ethylene oxide and the like, (b) a diol compound with a molecular weight of 200 or less, (c) an organic polyisocyanate, and (d) a hydroxyl group-containing (meth)acrylate, (B) a compound containing an ethylenically unsaturated group other than the component (A), and (C) a photoinitiator.
  • A a urethane (meth)acrylate produced by reacting (a) a diol compound produced by reacting bisphenol A with ethylene oxide and the like, (b) a diol compound with a molecular weight of 200 or less, (c) an organic polyisocyanate, and (d) a hydroxyl group-containing (meth)acrylate, (B) a compound containing an eth
  • a translucent screen such as a Fresnel lens and a lenticular lens having a high refractive index and exhibiting excellent adhesion to diversified substrates, as well as superior abrasion resistance and restorability in the combinations of Fresnel lens and lenticular lens
  • a photocurable resin composition comprising (A) a urethane (meth)acrylate produced by reacting compounds which at least comprise a polyether diol compound with a number average molecular weight of 200 to 500 containing a structure selected from the group consisting of a tetramethyleneoxy structure, a propyleneoxy structure, and a 1 ,2-butyleneoxy structure in the molecule, an organic polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate, (B) a monofunctional (meth)acrylate, (B) a monofunctional (meth)acrylate
  • the present invention provides a photocurable resin composition
  • a photocurable resin composition comprising the following components (A), (B), and (C):
  • each R 1 individually represents a hydrogen atom or a methyl group
  • each R 2 individually represents an oxygen atom or sulfur atom
  • R 3 is a group -CH 2 -, -C(CH 3 ) 2 -, -S-, -SO-, or -SO 2 -
  • X 1 to X 4 individually represent a hydrogen atom, methyl group, or bromine atom
  • m and n individually represent a number from 1 to 9
  • R 4 represents a hydrogen atom or a methyl group
  • R 5 represents - (CH 2 CH 2 O) p -, -(CH(CH 3 )CH 2 O) q -, or -CH 2 CH(OH)CH 2 O- (wherein p and q represent integers from 0 to 10)
  • Y 1 to Y 3 individually represent a hydrogen atom, a bromine atom, an alkyl group having 1-10 carbon atoms, phenyl group, or -C(CH 3 ) 2 C 6 H 5 -;
  • the present invention further provides a photosensitive resin composition which may comprise, in addition to the components of the above photocurable resin composition, 0.001 to 10 parts by weight of polyoxyalkylene alkyl ether phosphate of the following formula (3) as component
  • R is an alkyl group or an alkyl-substituted phenyl group with the alkyl group having 1-20 carbon atoms, r is a number from 1 to 15, and A is -OH or R 8 O(CH 2 CH(R 7 )O) s -, wherein R 8 is an alkyl group or an alkyl-substituted phenyl group with the alkyl group having 1-20 carbon atoms, s is a number from 1 to 15, and R 7 represents a hydrogen atom or methyl group.
  • the present invention further provides optical parts comprising a cured product of the above photocurable resin composition.
  • the component (A) used in the photocurable resin composition of the present invention is preferably a urethane (meth)acrylate produced by reacting at least four compounds which preferably comprise a polyether diol compound with a number average molecular weight of 200 to 500 containing a structure selected from the group consisting of a tetramethyleneoxy structure, a propyleneoxy structure, and a 1 ,2-butyleneoxy structure in the molecule, preferably a diol compound represented by the following formula (1), but other than the above polyether diol compound, an organic polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate.
  • a urethane (meth)acrylate produced by reacting at least four compounds which preferably comprise a polyether diol compound with a number average molecular weight of 200 to 500 containing a structure selected from the group consisting of a tetramethyleneoxy structure, a propyleneoxy structure, and a 1 ,2-butyleneoxy
  • polytetramethylene glycol polypropylene glycol, and poly(1 ,2)- butylene glycol
  • binary copolymers such as a copolymer of tetrahydrofuran and propylene oxide, tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydrofuran and 3-methyltetrahydrofuran, tetrahydrofuran and ethylene oxide, or butene-1- oxide and ethylene oxide
  • ternary copolymers such as a copolymer of tetrahydrofuran, butene-oxide, and propylene oxide, propylene oxide, butene-1- oxide, and ethylene oxide, or tetrahydrofuran, butene-1 -oxide, and ethylene oxide, can be given.
  • a polyether diol produced by the ring-opening copolymerization of the above ion-polymerizable cyclic compounds and cyclic imines such as ethyleneimine, cyclic lactonic acids such as ⁇ -propyolactone and glycolic acid lactide, or dimethylcyclopolysiloxanes can also be used.
  • the ring-opening copolymers of the ion-polymerizable cyclic compounds may be either a random copolymer or a block copolymer.
  • the polystyrene-reduced number average molecular weight of these polyether diols determined by GPC is preferably from 200 to 500, preferably from 220 to 480, and still more preferably from 240 to 460.
  • the number average molecular weight is less than 200, it may be difficult for the cured products to exhibit satisfactory lens properties such as adhesion to substrates, abrasion resistance, and shape restorability. If more than 500, it may be difficult for a lens to maintain the proper shape when a load is applied.
  • PTG250, PTG400 manufactured by Hodogaya Chemical Co., Ltd.
  • K-4006, K-4007 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.
  • Sunnix PP-400 manufactured by Sanyo Chemical Industries, Ltd.
  • polyisocyanates having an aromatic ring such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1 ,4-xylylene diisocyanate, 1 ,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'- dimethylphenylene diisocyanate, and 4,4'-biphenylene diisocyanate can be given.
  • 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1 ,3-xylylene diisocyanate, and 1 ,4-xylylene diisocyanate are particularly preferable.
  • (meth)acrylate compounds such a compound are 4- hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2- hydroxybutyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 1 ,4- butanediol mono(meth)acrylate, 2-hydroxyalkyl(meth)acryloyl phosphate, 4- hydroxycyclohexyl(meth)acrylate, 1 ,6-hexanediol mono(meth)acrylate, neopentyl glycol mono
  • R 9 represents a hydrogen atom or a methyl group and v is a number from 1 to 15.
  • Compounds obtained by the addition reaction of (meth)acrylic acid and a compound containing a glycidyl group such as alkyl glycidyl ether, allyl glycidyl ether, and glycidyl (meth)acrylate can also be used. These hydroxyl group- containing (meth)acrylates may be used either individually or in combinations of two or more.
  • m and n in the formula (1) represent integers from 0 to 9, and preferably from 1 to 5.
  • a diol compound represented by the above formula (1), an organic polyisocyanate compound, and a hydroxyl group-containing (meth)acrylate for producing the urethane (meth)acrylate (A) are: a method of reacting the above polyether diol, the diol of the formula (1), the organic polyisocyanate compound, and the hydroxyl group-containing (meth)acrylate all together; a method of reacting the polyether diol with the organic polyisocyanate compound, then reacting with the diol of the formula (1), and finally reacting with the hydroxyl group-containing (meth)acrylate; a method of reacting the diol of the formula (1) with the organic
  • the method of reacting the organic polyisocyanate compound with the hydroxyl group-containing (meth)acrylate, then reacting with the polyether diol, and finally with the diol of the formula (1) is preferable for producing the urethane (meth)acrylate of the present invention.
  • the polyether diol When producing the urethane (meth)acrylate (A), it is preferable to add the polyether diol, and finally with the diol of the formula (1), organic polyisocyanate compound, and hydroxyl group-containing (meth)acrylate so that the isocyanate groups included in the organic polyisocyanate compound and the hydroxyl groups included in the hydroxyl group-containing (meth)acrylate are respectively 1.1-1.5 equivalents and 0.1-0.5 equivalent for one equivalent of the hydroxyl groups included in the polyether diol and the diol of the formula (1).
  • the urethane (meth)acrylate (A) most preferably contains the polyether diol and the diol of the formula (1) in the molecule by the reaction with the organic isocyanate compound.
  • the polyether diol and the diol of the formula (1) are used preferably at a proportion of 10-70 parts by weight and 30-90 parts by weight. If the urethane (meth)acrylate (A) does not contain either the polyether diol or the diol of the formula (1) in the molecule, the cured product may not satisfy the target characteristics such as a refractive index, modulus of elasticity, adhesion to substrates, and restorability from deformation, and therefore may not exhibit satisfactory performance as optical parts.
  • a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, and triethylenediamine-2-methyltriethyleneamine is usually used in an amount from 0.01 to 1 wt% of the total weight of the reactant.
  • the reaction is carried out preferably at 10-90°C, and particularly preferably at 30-80°C.
  • the number average molecular weight of the urethane (meth)acrylate (A) is preferably from 1 ,000 to 20,000, and particularly preferably from 1 ,500 to 15,000. If the number average molecular weight of the urethane (meth)acrylate (A) is less than 1 ,000, the modulus of elasticity of the cured product produced by curing the resin composition may increase extremely, thereby causing a break or crack when used as a lens. If the number average molecular weight exceeds 20,000, handling of the resin composition may become difficult due to the increased viscosity.
  • the urethane (meth)acrylate of the component (A) preferably contains both the polyether diol having a number average molecular weight of 200 to 500 and containing a tetramethyleneoxy structure in the molecule, and the polyether diol having a number average molecular weight of 200 to 500 and containing a 1 ,2-butyleneoxy structure in the molecule to obtain cured resin products with satisfactory adhesion to substrates, shape restorability, and breaking resistance.
  • the urethane (meth)acrylate of the component (A) preferably contains both the polyether diol with a number average molecular weight of 200 to 500 containing a tetramethyleneoxy structure in the molecule, and the polyether diol with a number average molecular weight of 200 to 500 containing a 1 ,2-butyleneoxy structure in the molecule.
  • Shape restorability of the cured resin products can be improved by using a polyether diol with a number average molecular weight of 200 to 500 containing a tetramethyleneoxy structure in the molecule as the component for the urethane (meth)acrylate (A).
  • Adhesion to substrates of the cured resin products is improved by using a polyether diol with a number average molecular weight of 200 to 500 containing a 1 ,2-butyleneoxy structure in the molecule as the component for the urethane (meth)acrylate (A).
  • the polyether diol with a number average molecular weight of 200 to 500 containing a tetramethyleneoxy structure in the molecule and the polyether diol with a number average molecular weight of 200 to 500 containing a 1 ,2-butyleneoxy structure in the molecule may be used as the components for the urethane (meth)acrylate (A) at any arbitrary ratio without a specific limitations, but giving due consideration to the balance between the required adhesion to substrates and shape restorability.
  • the urethane (meth)acrylate (A) is added to the resin composition in an amount preferably from 20 to 80 wt%, and still more preferably from 30 to 70 wt%.
  • the lower limit of this range must be observed for providing the cured product with appropriate mechanical properties such as mechanical strength and toughness, properties of preventing a break or crack when used as a lens sheet, and properties of ensuring easy restore of the lens shape when crushed.
  • the upper limit of this range must be observed for preventing the workability or applicability from decreasing due to the increased viscosity of the composition.
  • the monofunctional (meth)acrylate shown by the formula (2) is preferably used as the component (B) of the photocurable resin composition of the present invention.
  • component (B) examples include phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate, 3-(2-phenylphenyl-2- hydroxypropyl (meth)acrylate, (meth)acrylate of p-cumylphenol which is reacted with ethylene oxide, 2-bromophenoxyethyl (meth)acrylate, 2,4- dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, and the like. Of these, phenoxyethyl (meth)acrylate, phenoxyethoxyethyl (meth)acrylate, (meth)acrylate,
  • ARONIX M110, M101 , M5700, TO-1317 manufactured by Toagosei Co., Ltd.
  • Viscoat #192, #193, #220, 3BM manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • NK Ester AMP-10G, AMP-20G manufactured by Toagosei Co., Ltd.
  • the amount of the component (B) added to the composition is preferably 10-70 wt%, and particularly preferably 20-60 wt%.
  • the lower limit of this range is specified for providing both favourable adhesion to substrates and a sufficient refractive index.
  • the upper limit of this range is specified for obtaining preferred mechanical properties and applicability.
  • a compound having a (meth)acryloyl group or a vinyl group other than the component (B) can be used as an optional component (hereinafter referred to as "unsaturated monomer").
  • unsaturated monomer a monofunctional monomer and a polyfunctional monomer can be used.
  • a vinyl monomer such as N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, and vinylpyridine
  • (meth)acrylate methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone(meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acryIamide, t- octyl(meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, N,N- diethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, hydroxy butyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and monofunctional monomers shown by formulas (5) and (6) can be given:
  • R 10 is a hydrogen atom or a methyl group
  • R 11 is an alkylene group having 2 to 8 carbon atoms
  • w is a number from 1 to 8.
  • R 12 and R 13 are individually a hydrogen atom or a methyl group, and R 14 is an alkylene group having 2 to 8 carbon atoms, and x is a number from 1 to 8.
  • Aronix M111 , M113, M117 manufactured by Toagosei Co., Ltd.
  • LA IBXA
  • Viscoat #190, #2000 manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Light Acrylate EC-A, PO-A, NP-4EA, NP-8EA, HOA-MPL manufactured by Kyoeisha Chemical Co., Ltd.
  • KAYARAD TC110S manufactured by R629, R644 (manufactured by Nippon Kayaku Co., Ltd.)
  • FA-511A, 512A, 513A manufactured by Hitachi Chemical Co., Ltd.
  • VP manufactured by BASF
  • ACMO ACMO
  • acrylate compounds such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropanetrioxyethyl (meth)acrylate, tris(2- hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate,dipentaerythritol hexa(meth)acrylate, di(meth)
  • Yupimer UV SA1002, SA2007 manufactured by Mitsubishi Chemical Corp.
  • Viscoat #1 5, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA manufactured by Osaka Organic Chemical Industry Co., Ltd.
  • Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.
  • KAYARAD PET-30, TMPTA R-604, DPHA, DPCA-20,-30,-60,-120, HX-620, D- 310, D-330 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-208, M-210, M- 215, M-220, M-240, M-305, M-309, m-310, M-315, M-325 M-400 (manufactured by Toagosei Co., Ltd.), Ripoxy VR-77, VR-60, VR-90 (manufactured by Showa Highpolymer Co., Ltd.) and the like can be given.
  • the photocurable resin composition of the present invention is cured by radiation.
  • Radiation used herein includes ionizing radiation such as infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ -rays, ⁇ -rays, ⁇ -rays, and the like.
  • the photoinitiator which is the component (C) is required for curing the resin composition of the present invention and a photosensitizer is optionally added.
  • any compound which decomposes upon irradiation and generate radicals to initiate the polymerization can be used.
  • Examples of such compounds include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenyIacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'- dimethoxybenzophenone, 4,4'-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2- hydroxy-2- methylpropan-1 -one, 2-hydroxy-2-methyl-1 -phenylpropan-1 -one, thioxanthone, diethylthioxanthone, 2-isopropylthioxan
  • the photosensitizer triethylamine, diethylamine,
  • N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4- dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4- dimethylaminobenzoate, and the like can be given.
  • Ubecryl P102, 103, 104, 105 manufactured by UCB
  • Ubecryl P102, 103, 104, 105 manufactured by UCB
  • the optimum amount of the photoinitiator used to cure the resin composition of the present invention is from 0.01 to 10 wt%, and preferably from 0.5 to 7 wt% of the total amount of the composition.
  • the above upper limit is desirable in view of ensuring superior curing characteristics of the composition, mechanical and optical characteristics of cured products, and handling easiness; and the lower limit is desirable for preventing decrease in the curing speed.
  • a heat-polymerization initiator can be optionally added when curing the resin composition of the present invention.
  • Peroxides and azo compounds can be given as examples of preferable heat-polymerization initiators. Specific examples include benzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and the like.
  • polyoxyalkylene alkyl ether phosphate of the above formula (3) it is desirable to add a polyoxyalkylene alkyl ether phosphate of the above formula (3) to the resin composition of the present invention as the component (D) to improve releasability from a mold during continuous manufacture of cured products.
  • Polyoxyethylene alkyl ether phosphate, polyoxypropylene alkyl ether phosphate, polyoxyethylene alkyl-substituted phenyl ether phosphate, olyoxypropylene alkyl-substituted phenyl ether phosphate, and the like can be given as polyoxyalkylene alkyl ether phosphates used as the component (D).
  • polyoxyalkylene alkyl ether phosphate used as the component (D) are Plysurf AL, A-208S, A-208B, A208F, A-219B, M208F, A-215C, A-212C, A-217E (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Antox EHD-200, Newcol 1000FCP, 565-PS, 1120-PS, Paracol OP (manufactured by Nippon Nyukazai Co., Ltd.), and the like.
  • the amount of polyoxyalkylene alkyl ether phosphate used as the component (D) in the resin composition of the present invention is preferably from 0.001 to 10 parts by weight, and particularly preferably from 0.01 to 2 parts by weight, for 100 parts by weight of the components (A), (B), and (C). If less than 0.001 parts by weight, releasability from metal molds during continuous manufacture may be insufficient; if more than 10 parts by weight, liquid bleeds may appear on the surface of cured products, impairing external appearance of final products and performance of lenses.
  • Curable oligomers or polymers other than the above components may be added to the resin composition of the present invention insofar as the characteristics of the resin composition are not adversely affected.
  • curable oligomers or polymers polyurethane (meth)acrylate other than the component (A), polyester (meth)acrylate, epoxy (meth)acrylate, polyamide (meth)acrylate, siloxane polymers having a (meth)acryloyloxy group, and reactive polymers produced by reacting a copolymer of glycidyl methacrylate and other polymerizable monomers with (meth)acrylic acid can be given.
  • additives such as antioxidants, UV absorbers, light stabilizers, silane coupling agents, coating surface improvers, heat-polymerization inhibitors, leveling agents, surfactants, coloring agents, preservatives, plasticizers, lubricants, solvents, fillers, aging preventives, wettability improvers, and the like can be added as required.
  • antioxidants include Irganox1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Antigene P, 3C, FR, Sumiiizer GA-80 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like;
  • UV absorbers include Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 110, 501 , 202, 712, 704 (manufactured by Sypro Chemical Co., Ltd.), and the like;
  • examples of light stabilizers include Tinuvin 292, 144, 622LD (manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 (manufactured by Sankyo Co., Ltd.), Sumisorb TM-061 (manufactured by Sum
  • the resin composition of the present invention is manufactured by mixing the above components using a conventional method.
  • Viscosity of the resin composition of the present invention thus prepared is usually from 200 to 50,000 mPa s/25°C, and preferably from 500 to 30,000 mPa s/25°C. If the viscosity is too high, uneven coating or a crinkle occurs or the objective lens thickness cannot be secured, thereby resulting in inadequate lens performance. If the viscosity is too low, on the other hand, it is difficult to control the lens thickness and therefore to manufacture lenses with a uniform thickness. It is particularly preferable that the cured product prepared by curing the resin composition of the present invention by radiation have the following properties.
  • the cured product produces a temperature dependency curve of a loss tangent having at least two peaks or shoulders at a temperature range between -150 and 100°C when an oscillation frequency of 10 Hz is applied using a dynamic viscoelasticity measuring device.
  • a translucent screen such as a lens sheet is formed from the resin composition of which the cured product satisfies this property, such a translucent screen exhibits superior adhesion to substrates, shape restorability, and moderate mechanical properties. Therefore, the lens projection is protected from abrasion or fracture, or even if crushed, the original shape can be immediately restored.
  • the refractive index of the cured product at 25°C is preferably 1.54 or more, and still more preferably 1.55 or more. If the refractive index is less than 1.54, a translucent screen formed from the resin composition may exhibit insufficient frontal brightness.
  • a reaction vessel equipped with a stirrer was charged with 29.6 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.02 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C. 18.9 parts by weight of 2-hydroxy-3-phenyloxypropyl acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour. 34.2 parts by weight of polytetramethylene glycol with a number average molecular weight of 402 was then added and the mixture was reacted at 50°C for one hour.
  • a reaction vessel equipped with a stirrer was charged with 30.1 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.02 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C. 19.2 parts by weight of 2-hydroxy-3-phenyloxypropyl acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour. 33.1 parts by weight of poly(1,2)-butylene glycol with a number average molecular weight of 383 was then added and the mixture was reacted at 50°C for one hour.
  • a reaction vessel equipped with a stirrer was charged with 29.8 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.03 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C. 19.0 parts by weight of 2-hydroxy-3-phenyloxypropyl acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour.
  • a reaction vessel equipped with a stirrer was charged with 29.6 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.02 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C. 18.9 parts by weight of 2-hydroxy-3-phenyloxypropyl acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour. 51.5 parts by weight of polytetramethylene glycol with a number average molecular weight of 402 was then added and the mixture was reacted at 50-70°C for two hours. The reaction was terminated when the residual isocyanate was 0.1 part by weigh or less.
  • the resulting urethane acrylate is referred to as "A-4".
  • a reaction vessel equipped with a stirrer was charged with 42.88 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.03 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C. 19.08 parts by weight of 2-hydroxyethyl acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour. 5.09 parts by weight of ethylene glycol was then added and the mixture was reacted for one hour.
  • a reaction vessel equipped with a stirrer was charged with 15.4 parts by weight of 2,4-tolylene diisocyanate, 0.08 part by weight of di-n-butyltin dilaurate, and 0.02 part by weight of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C.
  • 13.1 parts by weight of 2-hydroxy-3-phenyloxypropyI acrylate was added dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was allowed to react at 30°C for one hour.
  • 59.4 parts by weight of polytetramethylene glycol with a number average molecular weight of 2018 was then added and the mixture was reacted at 50°C for one hour.
  • a reaction vessel equipped with a stirrer was charged with 36.12 wt% of 2,4-tolylene diisocyanate, 0.08 wt% of di-n-butyltin dilaurate, and 0.03 wt% of 2,6-di-t-butyl-p-cresol.
  • the mixture was cooled to 5-10°C.
  • To the mixture was added 23.04 wt% of 2-hydroxy-3-phenyloxypropyl acrylate dropwise while stirring so as to maintain the temperature at 30°C or lower. After the addition, the mixture was reacted for one hour at 30°C.
  • a reaction vessel equipped with a stirrer was charged with 20 parts by weight of "A-1" as the component (A), 36 parts by weight of phenoxyethyl acrylate (New Frontier PHE manufactured by Daiichi Kogyo Seiyaku Co, Ltd.) as the component (B), 3.5 parts by weight of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184 manufactured by Ciba Specialty Chemicals Co.) as the component (C), 0.2 part by weight of Plysurf A-208F (manufactured by Daiichi Kogyo Seiyaku Co, Ltd.) as the component (D), 12 parts by weight of an ethylene oxide addition compound of bisphenol A diacrylate (Viscoat #700 manufactured by Osaka Organic Chemical Industry, Ltd.), 6 parts by weight of tetraethylene glycol diacrylate (Light Acrylate 4EG-A manufactured by Kyoeisha Chemical Co, Ltd.), 2 parts by weight of SH-190 (a coating surface improver
  • liquid resin compositions were obtained by charging the reaction vessel with the components shown in Table 1 and reacting the components.
  • the viscosity, refractive index, adhesion to substrates, abrasion resistance, breaking resistance, and shape restorability of the test specimens were measured according to the following methods.
  • the viscosity of the liquid curable resin composition at 25°C was measured using a rotational viscometer according to JIS K7117.
  • the liquid curable resin composition was applied onto a glass plate to a thickness of about 200 ⁇ m using a 15 mill applicator bar.
  • the composition was irradiated with ultraviolet rays at a dose of 1.0 J/cm 2 in air to obtain a cured film.
  • the cured film was removed from the glass plate for use as a test specimen.
  • the refractive index at 25°C of the test specimen prepared above was measured according to JIS K7105 using an Abbe's refractometer (manufactured by Atago Co, Ltd.).
  • Liquid curable resin compositions shown in Table 1 were fed to the space between a Fresnel lens mold and a PMMA substrate (10 cm x 10 cm) with a thickness of 2 mm, and the PMMA substrate was pressed to prepare resin composition layers with a uniform thickness.
  • the resin layer was cured by irradiating with ultraviolet rays at a dose of 1.0 J/cm 2 from the side of the substrate.
  • the cured resin (hereinafter referred to as "lens substrate”) was removed from the mold by hand.
  • Lens substrates removed from the above lens molds were evaluated by measuring adhesivness with the MS substrates by a cross cut peeling test according to JIS K5400.
  • a lens for which the square was not peeled from the MS substrate but adhered perfectly to the MS substrate was rated as AAA, a lens for which part of the squares was peeled from the MS substrate was rated as BBB, and a lens for which all the squares were peeled from the MS substrate was rated as CCC.
  • the lens substrate removed from the mold was placed on a plane with the lens surface upside, on which a PMMA lenticular lens (radius 0.5 mm, pitch 0.7 mm, 10 cm x 10 cm, manufactured by Nihon Tokushu Kougaku Jushi Co, Ltd.) was layered with the hill of the lenses perpendicularly crossing. Then, a load of 500 g was applied. The surface conditions of the lens was observed after oscillating the lens substrate for 5 minutes at the oscillating cycle resulting in a back-and-forth movement twice a second at an interval of 4 cm at - 20°C.
  • a lens with no abrasion or broken parts was rated as AAA, a lens with some abrasion or broken parts was rated as BBB, and a lens with abrasion or broken parts over the entire surface was rated as CCC.
  • Shape restorability A metal ball indenter with a diameter of 0.4 mm was pressed into the lens surface of the lens substrate removed from the lens mold with a 30 g load for one minute. The period of time required for the ball mark on the lens surface to disappear was measured at 23°C. A lens for which the ball mark disappeared within 5 minutes was rated as AAA, a lens for which the ball mark disappeared within 10 minutes was rated as BBB, a lens for which the ball mark disappeared later than 10 minutes but within one hour was rated CCC, and a lens for which the ball mark did not disappear after one hour was evaluated as DDD.
  • B-3 Isobornyl acrylate ("IBXA” manufactured by Osaka Organic Chemical Industry Co, Ltd.)
  • E-2 Ethylene glycol diacrylate ("Light Acrylate 4EGA” manufactured by Kyoeisha)
  • the photocurable resin composition comprising the component (A) in the amount of 20-80 wt%.
  • the photocurable resin composition comprising the component (B) in the amount of 10-70 wt%.
  • the photocurable resin composition comprising the component (C) in the amount of 0.01-10 wt%.
  • the photocurable resin composition having viscosity of 500-30,000 mPa-s at 25°C.
  • the liquid curable resin composition of the present invention provides a cured product exhibiting a high refractive index, superior adhesion to the substrate, restorability, and abrasion resistance. Therefore the resin composition is suitable for manufacturing optical parts such as a lens sheet.

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition de résine photodurcissable comprenant les composants suivants : (A) un (méth)acrylate d'uréthane produit par mise en réaction de composés, dont au moins un composé diol de polyéther ayant un poids moléculaire moyen en nombre compris entre 200 et 500 renfermant une structure sélectionnée dans le groupe comprenant une structure tétraméthylèneoxy, une structure propylèneoxy, et une structure 1,2-butylèneoxy dans la molécule, un composé polyisocyanate organique, et un (méth)acrylate renfermant un groupe hydroxy, (B) un (méth)acrylate monofonctionnel et (C) un photoamorceur. L'invention concerne également des éléments et des produits optiques utilisés dans des téléviseurs à rétroprojection.
PCT/NL2001/000714 2000-10-03 2001-10-01 Composition de resine photodurcissable et materiau optique WO2002029448A2 (fr)

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Cited By (4)

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WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique
WO2006022545A1 (fr) * 2004-08-25 2006-03-02 Jsr Corporation Formulation de résine liquide durcissable
WO2006068465A1 (fr) * 2004-12-24 2006-06-29 Jsr Corporation Composition formant un élément optique en résine durcissable sous un rayonnement et élément optique
US7790266B2 (en) 2000-11-09 2010-09-07 Reflexite Corporation Reboundable optical structure

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JP4531620B2 (ja) * 2005-04-14 2010-08-25 日本合成化学工業株式会社 ウレタン（メタ）アクリレート系化合物及びそれを用いた活性エネルギー線硬化型樹脂組成物、並びにコーティング剤
JP2006308840A (ja) * 2005-04-28 2006-11-09 Nippon Kayaku Co Ltd 光学レンズ用高屈折率樹脂組成物およびその硬化物
WO2008117854A1 (fr) 2007-03-27 2008-10-02 Dai Nippon Printing Co., Ltd. Élément optique en forme de feuille, composition de résine pour feuille optique, feuille optique et procédé de fabrication de la feuille optique
JP2017132859A (ja) * 2016-01-26 2017-08-03 アイカ工業株式会社 プリズム形成用光硬化性樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7790266B2 (en) 2000-11-09 2010-09-07 Reflexite Corporation Reboundable optical structure
WO2004033511A1 (fr) * 2002-10-08 2004-04-22 Dsm Ip Assets B.V. Composition de resine photodurcissable et matiere optique
WO2006022545A1 (fr) * 2004-08-25 2006-03-02 Jsr Corporation Formulation de résine liquide durcissable
WO2006068465A1 (fr) * 2004-12-24 2006-06-29 Jsr Corporation Composition formant un élément optique en résine durcissable sous un rayonnement et élément optique

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WO2002029448A3 (fr) 2002-08-08

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