WO2006068465A1 - Radiation-curable resin optical member forming composition and optical member - Google Patents
Radiation-curable resin optical member forming composition and optical member Download PDFInfo
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- WO2006068465A1 WO2006068465A1 PCT/NL2005/000868 NL2005000868W WO2006068465A1 WO 2006068465 A1 WO2006068465 A1 WO 2006068465A1 NL 2005000868 W NL2005000868 W NL 2005000868W WO 2006068465 A1 WO2006068465 A1 WO 2006068465A1
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- Prior art keywords
- meth
- acrylate
- optical member
- bisphenol
- glycol
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- 0 CC(C(C(*)=C)=O)O*C(*OC(C)(C)C1OCC(*)(*)CO1)=O Chemical compound CC(C(C(*)=C)=O)O*C(*OC(C)(C)C1OCC(*)(*)CO1)=O 0.000 description 1
Classifications
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- 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
- G02B1/041—Lenses
-
- 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
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic 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
- C08G18/67—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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
Abstract
To provide a UV-curable resin composition useful for forming an optical member such as an optical lens, particularly a Fresnel lens of a micro-display type projection television. A radiation-curable resin optical member forming composition comprising (A) 5 to 70 wt% of a urethane (meth)acrylate having a structure shown by the following formula (1), and (B) 10 to 70 wt% of an ethylenically unsaturated group-containing compound other than the component (A). Formula (1) : [R1-O-CONH-R2-NHCO]n-R3 wherein R1 represents a (meth)acryloyl group or an alkyl group having 1 to 4 carbon atoms, R2 represents a divalent organic group having an aromatic ring, R3 represents an organic group having 2 to 20 carbon atoms and a valence of 2 to 6, and n represents an integer from 2 to 6; R1S may differ from each other on condition that 40 to 85 mol% of R1 is a (meth)acryloyl group and 15 to 60 mol% of R1 is an alkyl group having 1 to 4 carbon atoms.
Description
RADIATION-CURABLE RESlN OPTICAL MEMBER FORMING COMPOSITION AND
OPTICAL MEMBER
The present invention relates to a radiation-curable resin composition. More particularly, the present invention relates to a radiation-curable resin composition useful for forming an optical member such as a lens of a lens sheet (e.g. a prism lens sheet used for a backlight of a liquid crystal display device, or a Fresnel lens sheet or a lenticular lens sheet used for a screen of a projection TV) or a backlight using such a sheet, and to an optical member including a cured product of the composition.
Lenses such as a Fresnel lens or a lenticular lens have been produced by a pressing method or a casting method. However, these methods require a long time to manufacture a lens which exhibits poor productivity. In recent years, a method of producing a lens using a UV-curable resin has been studied in order to solve such a problem. Specifically, a UV-curable resin composition is poured into a space between a lens-shaped mold and a transparent resin substrate, and the composition is cured by applying ultraviolet rays from the substrate side to produce a lens in a short time. In recent years, along with a reduction in thickness and an increase in size of a projection television or a video projector, various lens forming resins have been proposed and studied in order to provide a lens with various properties such as a high refractive index and mechanical properties. For example, a UV-curable resin composition containing a urethane (meth)acrylate, an ethylenically unsaturated group- containing monomer, and a photoinitiator has been proposed (see JP-A-4-288314, JP- A-5-255464 and J P-A-2001-200022). However, such a known UV-curable resin composition cannot produce a cured product which satisfies properties required for a lens, such as a high refractive index, adhesion to a plastic substrate particularly in a wet-heat environment, or removability from a mold.
The inventors of the present invention have conducted extensive studies in order to solve the above-described problem of the known resin composition. As a result, the inventors found that an optical member, particularly a transparent screen such as a Fresnel lens or a lenticular lens, having a high refractive index and exhibiting excellent adhesion to a plastic substrate in a wet-heat environment can be obtained by producing a cured product using a radiation-curable resin composition including (A) a methanol-terminated urethane (meth)acrylate and (B) an ethylenically unsaturated group-containing compound other than the component (A) in specific
amounts. This finding has led to the completion of the present invention.
Specifically, the present invention provides the following radiation- curable resin optical member forming composition and a cured product obtained by curing the composition. 1. A radiation-curable resin optical member forming composition comprising:
(A) 5 to 70 wt% of a urethane (meth)acrylate having a structure shown by the following formula (1),
[R1-O-CONH-R2-NHCO]n-R3 (1)
wherein R1 represents a (meth)acryloyl group or an alkyl group having 1 to 4 carbon atoms, R2 represents a divalent organic group having an aromatic ring, R3 represents an organic group having 2 to 20 carbon atoms and a valence of 2 to 6, and n represents an integer from 2 to 6; R1S may differ from each other on condition that 40 to 85 mol% of R1 is a
(meth)acryloyl group and 15 to 60 mol% of R1 is an alkyl group having 1 to 4 carbon atoms; and
(B) 10 to 70 wt% of an ethylenically unsaturated group-containing compound other than the component (A). 2. The radiation-curable resin optical member forming composition according to
[1], wherein R3 in the formula (1) is derived from a polyol including at least one compound selected from the group consisting of bisphenol A polyethoxy glycol, bisphenol A polypropoxy glycol, bisphenol A polyethoxypropoxy glycol, bisphenol F polyethoxy glycol, bisphenol F polypropoxy glycol, bisphenol F polyethoxypropoxy glycol, bisphenol S polyethoxy glycol, bisphenol S polypropoxy glycol, and bisphenol S polyethoxypropoxy glycol as the major component.
3. The radiation-curable resin optical member forming composition according to [1] or [2], wherein R3 in the formula (1) is an alkylene oxide addition diol of bisphenol A shown by the following formula (2),
1.53 or more at 250C. 6. The radiation-curable resin optical member forming composition according to any of [1] to [5], wherein the optical member is an optical lens. 7. An optical member comprising a cured product obtained by applying radiation to the radiation-curable resin optical member forming composition according to any of [1] to [6].
8. The optical member according to [7], which is an optical lens.
9. The optical member according to [8], which is a Fresnel lens of a micro- display type projection television.
10. The optical member according to any of [7] to [9], wherein the cured product adheres to a transparent plastic substrate mainly formed of a methyl methacrylate-styrene copolymer.
According to the present invention, a radiation-curable resin optical member forming composition exhibiting a high refractive index and excellent adhesion to a plastic substrate (particularly a methyl methacrylate-styrene copolymer) and a cured product obtained curing the composition can be provided.
According to the present invention, a cured product suitably used as an optical member exhibiting a high refractive index and excellent adhesion to a plastic substrate, particularly as a Fresnel lens of a micro-display type projection television can be provided.
The urethane (meth)acrylate (A) used in the radiation-curable resin optical member forming composition of the present invention (hereinafter may be referred to as "composition of the present invention") has a structure shown by the following formula (1) (hereinafter referred to as "partially-alcohol-terminated urethane (meth)acrylate").
[R1-O-CONH-R2-NHCO]n-R3 (1)
In the formula (1), R1 represents a (meth)acryloyl group or an alkyl group having 1 to 4 carbon atoms. When R1 represents a (meth)acryloyl group, R1 is
derived from (b) a hydroxyl group-containing (meth)acrylate, and, when R1 represents an alkyl group having 1 to 4 carbon atoms, R1 is derived from (d) an alcohol having 1 to 4 carbon atoms. R2 represents a divalent organic group having an aromatic ring, and is derived from (c) a diol. R3 represents an organic group having 2 to 20 carbon atoms and a valence of 2 to 6, and is derived from (c) a polyol. n represents an integer from 2 to 6. R1S may differ from each other on condition that 40 to 85 mol% of R1 is a (meth)acryloyl group and 15 to 60 mol% of R1 is an alkyl group having 1 to 4 carbon atoms.
The partially-alcohol-terminated urethane (meth)acrylate (A) used in the present invention is usually obtained by reacting the hydroxyl group-containing (meth)acrylate (a), the organic polyisocyanate (b), the polyol (c), and the alcohol (d) having 1 to 4 carbon atoms.
As examples of the hydroxyl group-containing (meth)acrylate, 2- 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(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolethane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, (meth)acrylate shown by the following formula (3), and the like can be given.
(3)
wherein R1 represents a hydrogen atom or a methyl group, and v represents an integer from 1 to 15.
A compound obtained by the addition reaction of (meth)acrylic acid and a glycidyl group-containing compound, such as an alkyl glycidyl ether, allyl glycidyl ether, or glycidyl (meth)acrylate, may also be used. The hydroxyl group-containing (meth)acrylate may be used either individually or in combination of two or more.
As examples of the organic polyisocyanate (b), 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, 4,4'-biphenylene diisocyanate, and the like can be given. It is preferable to use 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, or 1,4-xylylene diisocyanate. As examples of the polyol (c), ethylene glycol, propylene glycol, 1 ,4- butanediol, neopentyl glycol, 3-methyl-1 ,5-pentanediol, 1 ,3-butanediol, cyclohexanedimethylol, tricyclodecanedimethylol, 1 ,6-hexanediol, 2-butyl-2-ethyl- propanediol, bisphenol A polyethoxy glycol, bisphenol A polypropoxy glycol, bisphenol A polyethoxypropoxy glycol, bisphenol F polyethoxy glycol, bisphenol F polypropoxy glycol, bisphenol F polyethoxypropoxy glycol, bisphenol S polyethoxy glycol, bisphenol S polypropoxy glycol, bisphenol S polyethoxypropoxy glycol, polytetramethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene butylene glycol, polycaprolactonediol, polyesterdiol, polycarbonatediol, and the like can be given.
It is preferable to use at least one compound selected from bisphenol A polyethoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol A polypropoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol A polyethoxypropoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol F polyethoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol F polypropoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol F polyethoxypropoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol S polyethoxy glycol (average degree of polymerization n is preferably 2 to 40), bisphenol S polypropoxy glycolglycol (average degree of polymerization n is preferably 2 to 40), and bisphenol S polyethoxypropoxy glycol (average degree of polymerization n is preferably 2 to 40) from the viewpoint of the refractive index.
An alkylene oxide addition diol of bisphenol A shown by the following formula (2) is a particularly preferable polyol.
( 2 )
wherein m represents an integer from 1 to 3, and preferably 1 to 2.
As commercially available products of the alkylene oxide addition diol of bisphenol A, DB400 (manufactured by NOF Corporation; m=1.5) and the like can be
given.
The alcohol (d) having 1 to 4 carbon atoms is added to block a part of the terminals of the resulting urethane (meth)acrylate so that the urethane (meth)acrylate does not take part in the polymerization reaction for curing the resin composition of the present invention. As the component (d), methanol is preferable. The adhesion to a plastic substrate can be improved by blocking a part of the terminals of the urethane (meth)acrylate, although the mechanism is not known.
The hydroxyl group-containing (meth)acrylate (a) containing a hydroxyl group which may react with an isocyanate group and the alcohol (d) having 1 to 4 carbon atoms used as the raw materials for the partially-alcohol-terminated urethane (meth)acrylate must be reacted at a molar ratio of the hydroxyl group- containing (meth)acrylate (a) to the alcohol (d) having 1 to 4 carbon atoms in the range of 85:15 to 40:60. The molar ratio is preferably in the range of 85:15 to 70:30, and particularly preferably 76:24. If the molar ratio is outside the above range, the adhesion to a substrate may decrease.
The partially-alcohol-terminated urethane (meth)acrylate (A) may be produced by a method of reacting the polyol and the organic polyisocyanate, and reacting the resulting product with the hydroxyl group-containing (meth)acrylate and the alcohol having 1 to 4 carbon atoms; a method of reacting the organic polyisocyanate, the hydroxyl group-containing (meth)acrylate, and the alcohol having 1 to 4 carbon atoms, and reacting the resulting product with the polyol; or a method of reacting the polyol, the organic polyisocyanate, the hydroxyl group-containing (meth)acrylate, and the alcohol having 1 to 4 carbon atoms all together. It is preferable to obtain the partially-alcohol-terminated urethane (meth)acrylate used in the present invention by the method of reacting the organic polyisocyanate, the hydroxyl group-containing
(meth)acrylate, and the alcohol having 1 to 4 carbon atoms, and reacting the resulting product with the polyol.
When producing the partially-alcohol-terminated urethane (meth)acrylate (A), the hydroxyl group-containing (meth)acrylate, the organic polyisocyanate, the polyol, and the alcohol having 1 to 4 carbon atoms are preferably used in such amounts that the isocyanate groups in the organic polyisocyanate and the hydroxyl groups in the hydroxyl group-containing (meth)acrylate and the alcohol having 1 to 4 carbon atoms are respectively 1.1 to 2 equivalents and 0.1 to 1 equivalent for one equivalent of the hydroxyl groups in the polyol. It is particularly preferably to use the hydroxyl group-containing (meth)acrylate, the organic polyisocyanate, the polyol, and the alcohol having 1 to 4 carbon atoms in such amounts that the isocyanate
groups in the organic polyisocyanate and the hydroxyl groups in the hydroxyl group- containing (meth)acrylate and the alcohol having 1 to 4 carbon atoms are respectively 1.3 to 2 equivalents and 0.3 to 1 equivalent for one equivalent of the hydroxyl groups in the polyol. If the amounts are outside the preferable range, it is difficult to handle the composition in a liquid state due to an increase in viscosity or the like.
When producing the partially-alcohol-terminated urethane (meth)acrylate (A), a urethanization catalyst such as copper naphthenate, cobalt naphthenate, zinc naphthenate, di-n-butyltin dilaurate, triethylamine, or triethylenediamine-2-methyltriethyleneamine is usually used in an amount of 0.01 to 1 wt% of the total amount of the reactants. The reaction is carried out at a temperature of preferably 10 to 900C, and particularly preferably 30 to 8O0C.
The number average molecular weight of the partially-alcohol- terminated urethane (meth)acrylate (A) is preferably 500 to 20,000, and particularly preferably 1 ,000 to 15,000. If the number average molecular weight of the partially- alcohol-terminated urethane (meth)acrylate (A) is less than 500, a cured product obtained by curing the resin composition exhibits poor adhesion to a substrate. If the number average molecular weight exceeds 20,000, it may be difficult to handle the resin composition due to an increase in viscosity.
The partially-alcohol-terminated urethane (meth)acrylate (A) is added to the resin composition in an amount of preferably 5 to 70 wt%, and particularly preferably 10 to 60 wt%. It is preferable that the lower limit be in the above range in order to provide the resulting cured product with moderate mechanical properties such as toughness. It is preferable that the upper limit be in the above range in order to prevent a decrease in workability and applicability due to an increase in the viscosity of the composition.
The component (B) used in the radiation-curable resin composition of the present invention is an ethylenically unsaturated group-containing compound other than the component (A). A compound containing a (meth)acryloyl group or a vinyl group (hereinafter called "unsaturated monomer") may be used as the component (B). As such a unsaturated monomer, a monofunctional monomer or a polyfunctional monomer may be used.
As examples of the monofunctional monomer, vinyl monomers such as N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, and vinylpyridine, phenoxyethyl (metha)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 reacted with ethylene oxide, 2-bromophenoxyethyl (meth)acrylate, 2,4- dibromophenoxyethyl (meth)acrylate, 2,4,6-tribromophenoxyethyl (meth)acrylate, phenoxy (meth)acrylate modified with two mol or more of ethylene oxide or propylene oxide, isobornyl (meth)acrylate, bomyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, acryloylmorpholine, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl
(meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, steary! (meth)acrylate, isostearyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, diacetone(meth)acrylamide, isobutoxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylarnide, 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, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, compounds shown by the following formulas (4) and (5), and the like can be given.
(4)
wherein R5 represents a hydrogen atom or a methyl group, R6 represents an alkylene group having 2 to 8 carbon atoms, and w represents an integer from 1 to 8.
wherein R7 and R9 individually represent a hydrogen atom or a methyl group, R8 represents an alkylene group having 2 to 8 carbon atoms, and x represents an integer from 1 to 8.
As examples of the polyfunctional monomer, 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, ths(acryloyloxy)isocyanurate, bis(hydroxymethyl)tricyclodecane di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, di(meth)acrylate of polyethylene oxide or propylene oxide addition diol of bisphenol A, di(meth)acrylate of ethylene oxide or propylene oxide addition diol of hydrogenated bisphenol A, epoxy(meth)acrylate obtained by addition of
(meth)acrylate to diglycidyl ether of bisphenol A, Methylene glycol divinyl ether, and the like can be given.
As examples of commercially available products of the monofunctional monomer, Aronix MI 01, M102, M110, M111 , M113, M117, M5700, TO- 1317, M120, M150, M156 (manufactured by Toagosei Co., Ltd.), LA, IBXA1 2-MTA, HPA, Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, #2150 (manufactured by Osaka Organic Chemical Industry, Ltd.), Light Aery late BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, Epoxy Ester M-600A (manufactured by Kyoeisha Chemical Co., Ltd.), Kayarad TC11OS, R-564, R-128H (manufactured by Nippon Kayaku Co., Ltd.), NK Ester AMP- 1OG, AMP-20G (manufactured by Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (manufactured by Hitachi Chemical Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), VP (manufactured by BASF), ACMO, DMAA, DMAPAA (manufactured by Kohjin Co., Ltd.), and the like can be given.
As examples of commercially available products of the polyfunctional monomer, Yupimer UV SA1002, SA2007 (manufactured by Mitsubishi Chemical Corp.), Viscoat #195, #230, #215, #260, #335HP, #295, #300, #360, #700, GPT, 3PA
(manufactured by Osaka Organic Chemical Industry, 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 component (B) is used in an amount of preferably 10 to 70 wt%, and particularly preferably 20 to 60 wt% of the total amount of the composition. It is preferable that the lower limit be within the above range from the viewpoint of the viscosity of the composition and the refractive index of the cured product. It is preferable that the upper limit be within the above range in order to ensure sufficient mechanical properties and applicability.
The radiation-curable resin composition of the present invention is cured by applying radiation. Radiation used herein refers to infrared rays, visible rays, ultraviolet rays, ionizing radiation such as X-rays, electron beams, α-rays, β-rays, and γ-rays. Light such as ultraviolet rays is conveniently used. A photoinitiator (C) is arbitrarily added to initiate the photocuring reaction, and a photosensitizer may also be added, as required. As the photoinitiator, a compound which decomposes upon irradiation and generates radicals to initiate polymerization may be used. As examples of the photoinitiator, acetophenone, acetophenone benzyl ketal, 1 -hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 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- isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio)phenyl]-2- morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6- dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and the like can be given.
As examples of commercially available products of the photoinitiator (C), lrgacure 184, 369, 651 , 500, 819, 907, 784, 2959, CGM 700, CGM 750, CGM 850, CG24-61 , Darocur 1116, 1173 (manufactured by Ciba Specialty Chemicals K.K.), Lucirin TPO, LR8893, LR8970 (manufactured by BASF), Ubecryl P36 (manufactured by UCB), and the like can be given.
As examples of 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. As examples of commercially available products of the photosensitizer, Ubecryl P102, 103, 104, 105 (manufactured by UCB), and the like can be given.
The optimum amount of the photoinitiator (C) used to cure the resin composition of the present invention is preferably 0.01 to 10 wt%, and particularly preferably 0.5 to 7 wt% of the total amount of the composition. The upper limit is preferable from the viewpoint of the curing properties of the composition, the mechanical and optical properties and handling of the cured product. The lower limit is preferable in order to prevent a decrease in curing speed.
A heat polymerization initiator may also be added as required when curing the resin composition of the present invention. As examples of preferable heat polymerization initiators, peroxides and azo compounds can be given. As specific examples of the heat polymerization initiator, benzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and the like can be given.
A curable oligomer or polymer other than the above-described components may optionally be added to the resin composition of the present invention insofar as the properties of the resin composition are not adversely affected. As examples of such a curable oligomer or polymer, polyurethane (meth)acrylate other than the component (A), polyester (meth)acrylate, epoxy (meth)acrylate, polyamide (meth)acrylate, a siloxane polymer containing a (meth)acryloyloxy group, a reactive polymer produced by reacting a copolymer of glycidyl methacrylate and another polymerizable monomer with (meth)acrylic acid, and the like can be given. Additives such as an antioxidant, UV absorber, light stabilizer, silane coupling agent, coating surface improver, heat polymerization inhibitor, leveling agent, surfactant, coloring agent, preservative, plasticizer, lubricant, release agent, solvent, filler, aging preventive, and wettability improver may optionally be added in addition to the above-described components. As examples of the antioxidant, Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals K. K.), Antigene P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like can be given. As examples of the UV absorber, Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Specialty Chemicals K.K.), Seesorb 102, 103, 110, 501, 202, 712, 704 (manufactured by Shipro Kasei Kaisha, Ltd.), and the like can be given. As examples of the light stabilizer, Tinuvin 292, 144, 622LD (manufactured by Ciba
Specialty Chemicals K. K.), Sanol LS770 (manufactured by Sankyo Co., Ltd.), Sumisorb
TM-061 (manufactured by Sumitomo Chemical Industries Co., Ltd.), and the like can be given. As examples of the silane coupling agent, γ-aminopropyltriethoxysilane, γ~ mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane, and commercially available products such as SH6062, SH6030 (manufactured by Dow Coming Toray Silicone Co., Ltd.), and KBE903, KBE603, KBE403 (manufactured by Shin-Etsu Chemical Co., Ltd.) can be given. As examples of the coating surface improver, silicone additives such as dimethylsiloxane polyether and commercially available products such as DC-57, DC-190 (manufactured by Dow-Corning), SH-28PA, SH-29PA, SH-30PA, SH-190 (manufactured by Dow Coming Toray Silicone Co., Ltd.), KF351 , KF352, KF353, KF354 (manufactured by Shin-Etsu Chemical Co., Ltd.), and L- 700, L-7002, L-7500, FK-024-90 (manufactured by Nippon Unicar Co., Ltd.) can be given.
The resin composition of the present invention may be prepared by mixing the above-described components by a known method. The viscosity of the resin composition of the present invention thus prepared is usually 200 to 50,000 mPa-s/25°C, and preferably 500 to 30,000 mPa s/25°C. If the viscosity of the composition is too great, uneven application or a winding may occur when producing a lens, or a desired lens thickness may not be obtained, so that sufficient lens performance may not be obtained. If the viscosity is too low, it becomes difficult to control the lens thickness, so that a lens having a uniform thickness may not be formed.
The refractive index of the cured product of the composition at 250C is preferably 1.53 or more, and still more preferably 1.54 or more. If the refractive index is less than 1.53, a sufficient luminance may not be obtained when forming a transmission type screen using the resin composition.
A cured product obtained by applying radiation to the resin composition of the present invention is useful as an optical member such as a lens of a prism lens sheet, Fresnel lens sheet, or lenticular lens sheet, or a backlight using such a sheet. The cured product is particularly useful as an optical lens. In particular, an optical lens produced by pouring the radiation-curable resin composition into the space between a mold with a lens shape and a transparent plastic substrate, and curing the composition by applying ultraviolet rays from the side of the substrate is preferable. Therefore, an optical lens obtained by the present invention is preferably a lens in which the cured product of the present invention adheres to a transparent plastic substrate. As the transparent plastic substrate, a polymethyl methacrylate (PMMA) substrate and a methyl methacrylate-styrene copolymer (MS) substrate can be given.
An MS substrate is preferable as the transparent plastic substrate.
Examples
The present invention is described below in more detail by way of examples. However, the present invention is not limited to the following examples.
Synthesis Example 1 : synthesis of urethane (metrOacrylate
A reaction vessel equipped with a stirrer was charged with 32.52 wt% of 2,4-tolylene diisocyanate, 0.08 wt% of di-n-butyltin dilaurate, and 0.02 wt% of 2,6-di- t-butyl-p-cresol. Then, 10.84 wt% of 2-hydroxyethyl acrylate was added dropwise to the mixture with stirring while maintaining the solution temperature at 3O0C or less. After the addition, the mixture was allowed to react at 3O0C for one hour. After the addition of 56.64 wt% of bisphenol A polypropoxy glycol ("DB400" manufactured by NOF Corporation), the mixture was allowed to react at 50 to 7O0C for two hours. The reaction was terminated when the residual isocyanate content became 0.1 wt% or less. The resulting urethane acrylate is referred to as "oligomer A-1".
Synthesis Example 2: synthesis of 24% methanol-terminated urethane (meth)acrylate 24% methanol-terminated urethane (meth)acrylate was synthesized in the same manner as in Synthesis Example 1 except for adding 0.73 wt% of methanol together with 2,4-tolylene diisocyanate and using 33.15 wt% of 2,4-tolylene diisocyanate, 8.40 wt% of 2-hydroxyethyl acrylate, and 57.72 wt% of bisphenol A polypropoxy glycol. The resulting 24% methanol-terminated urethane acrylate is referred to as "oligomer A-2". The number of moles of methanol was 24% of the total number of moles of 2-hydroxyethyl acrylate and methanol.
Synthesis Example 3: synthesis of 12% methanol-terminated urethane (meth)acrylate 12% methanol-terminated urethane (meth)acrylate was synthesized in the same manner as in Synthesis Example 1 except for adding 0.36 wt% of methanol together with 2,4-tolylene diisocyanate and using 32.83 wt% of 2,4-tolylene diisocyanate, 9.63 wt% of 2-hydroxyethyl acrylate, and 57.14 wt% of bisphenol A polypropoxy glycol (average degree of polymerization: m=3). The resulting 12% methanol-terminated urethane acrylate is referred to as "oligomer A-3". The number of moles of methanol was 12% of the total number of moles of 2-hydroxyethyl acrylate and methanol.
Example 1
A reaction vessel equipped with a stirrer was charged with 36 wt% of the oligomer A-2 as the component (A), 10 wt% of dipentaerythritol hexacrylate as the component (B), 14 wt% of tripropylene glycol diacrylate, 10 wt% of ethylene oxide addition acrylate of bisphenol A, 30 wt% of phenoxyethyl acrylate, and 3 wt% of 1- hydroxycyclohexyl phenyl ketone as the component (C). After the addition of additives shown in Table 1 , the mixture was stirred at 50 to 6O0C for one hour to obtain a homogenous curable liquid resin composition.
In Example 2 and Comparative Examples 1 and 2, a reaction vessel was charged with components shown in Table 1 to obtain each curable liquid resin composition. The amount of components shown in Table 1 is indicated as part by weight.
A specimen was prepared by the following method using the curable liquid resin composition obtained in the example. The adhesion to a substrate was measured as described below.
Adhesion to substrate: the resin composition was applied to a mold with a Fresnel lens shape (hereinafter called "lens mold"). The resin composition was covered with a methyl methacrylate-styrene copolymer (MS) substrate (10x10 cm) with a thickness of 1.8 mm so that bubbles were not formed. The MS substrate was pressed so that the resin composition layer had a specific thickness (100 μm). Then, the resin layer was cured by applying ultraviolet rays at a dose of 1.0 J/cm2 from the side of the substrate, and the cured resin (hereinafter called "lens substrate") was removed from the mold by hand. The lens substrate removed from the lens mold was evaluated by removing the lens from the MS substrate at the interface there between using a cutter knife and by measuring the adhesion to the MS substrate by a cross-cut peeling test according to JIS K 5400. A case where the resin was not removed using the cutter and all the squares remained adhering to the MS substrate was evaluated as "Excellent", a case where a part of the resin was removed using the cutter but all the squares remained adhering to the MS substrate was evaluated as "Good", a case where some of the squares were removed from the MS substrate was evaluated as "Fair", and a case where all the squares were removed from the MS substrate was evaluated as "Bad".
Table 1
Dipentaerythritol hexaacrylate ("Kayarad DPHA" manufactured by Nippon Kayaku Co., Ltd.)
Tripropylene glycol diacrylate ("KS-TPGDA" manufactured by Nippon Kayaku Co., Ltd.) Ethylene oxide addition acrylate of bisphenol A ("Viscoat #700" manufactured by Osaka Organic Chemical Industry, Ltd.)
Phenoxyethyl acrylate ("New Frontier PHE" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Irganox 1035: 2,2'-thiodiethyl-bis-[3,5-di-t-butyl-4-hydroxyphenyl)propionate] (manufactured by Ciba Specialty Chemicals, K. K.) SH28PA (DC-190): dimethylpolysiloxane-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Silicone Co., Ltd.)
SH 190 (DC-57): dimethylpolysiloxane-polyoxyalkylene copolymer (manufactured by Dow Corning Toray Silicone Co., Ltd.) ADDI D700 (silicone-based product manufactured by Wacker Chemicals East Asia Ltd.) As is clear from the results shown in Table 1 , the radiation-curable resin compositions of Examples 1 and 2 using the 24% methanol-terminated urethane (meth)acrylate exhibit excellent initial adhesion. On the other hand, the radiation- curable resin composition of Comparative Example 1 using the urethane (meth)acrylate which is not terminated with methanol and the radiation-curable resin composition of Comparative Example 1 using the 12% methanol-terminated urethane (meth)acrylate exhibit poor initial adhesion.
The radiation-curable resin composition of the present invention produces a cured product exhibiting a high refractive index and excellent heat-moisture adhesion to a plastic substrate, and is suitable for producing an optical member, particularly an optical lens used for a transmission type screen such as a Fresnel lens and a lenticular lens.
The cured product obtained by the present invention is suitably used as an optical member exhibiting a high refractive index and excellent adhesion to a plastic substrate, particularly as a Fresnel lens of a micro-display type projection television.
Claims
1. A radiation-curable resin optical member forming composition comprising:
(A) 5 to 70 wt% of a urethane (meth)acrylate having a structure shown by the following formula (1),
[R1-O-CONH-R2-NHCO]n-R3 (1)
wherein R1 represents a (meth)acryloyl group or an alkyl group having 1 to 4 carbon atoms, R2 represents a divalent organic group having an aromatic ring, R3 represents an organic group having 2 to 20 carbon atoms and a valence of 2 to 6, and n represents an integer from 2 to 6;
R1S may differ from each other on condition that 40 to 85 mol% of R1 is a
(meth)acryloyl group and 15 to 60 mol% of R1 is an alkyl group having 1 to 4 carbon atoms; and (B) 10 to 70 wt% of an ethylenically unsaturated group-containing compound other than the component (A).
2. The radiation-curable resin optical member forming composition according to claim 1 , wherein R3 in the formula (1) is derived from a polyol including at least one compound selected from the group consisting of bisphenol A polyethoxy glycol, bisphenol A polypropoxy glycol, bisphenol A polyethoxypropoxy glycol, bisphenol F polyethoxy glycol, bisphenol F polypropoxy glycol, bisphenol F polyethoxypropoxy glycol, bisphenol S polyethoxy glycol, bisphenol S polypropoxy glycol, and bisphenol S polyethoxypropoxy glycol as the major component.
3. The radiation-curable resin optical member forming composition according to claim 1 or 2, wherein R3 in the formula (1) is an alkylene oxide addition diol of bisphenol A shown by the following formula (2),
wherein m represents an integer from 1 to 3.
4. The radiation-curable resin optical member forming composition according to any of claims 1 to 3, further comprising (C) 0.01 to 10 wt% of a photoinitiator.
5. The radiation-curable resin optical member forming composition according to any of claims 1 to 4, of which the cured product has a refractive index of 1.53 or more at 250C.
6. The radiation-curable resin optical member forming composition according to any of claims 1 to 5, wherein the optical member is an optical lens.
7. An optical member comprising a cured product obtained by applying radiation to the radiation-curable resin optical member forming composition according to any of claims 1 to 6.
8. The optical member according to claim 7, which is an optical lens.
9. The optical member according to claim 8, which is a Fresnel lens of a micro- display type projection television.
10. The optical member according to any of claims 7 to 9, wherein the cured product adheres to a transparent plastic substrate mainly formed of a methyl methacrylate-styrene copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004374706 | 2004-12-24 | ||
| JPJP2004-374706 | 2004-12-24 |
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| WO2006068465A1 true WO2006068465A1 (en) | 2006-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL2005/000868 WO2006068465A1 (en) | 2004-12-24 | 2005-12-16 | Radiation-curable resin optical member forming composition and optical member |
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| Country | Link |
|---|---|
| TW (1) | TW200634039A (en) |
| WO (1) | WO2006068465A1 (en) |
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| JP5187492B2 (en) * | 2007-11-22 | 2013-04-24 | Ｊｓｒ株式会社 | Curable resin composition, protective film and method for forming protective film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10324726A (en) * | 1997-05-23 | 1998-12-08 | Nippon Kayaku Co Ltd | Resin composition for optical material and its hardened material |
| WO2002029448A2 (en) * | 2000-10-03 | 2002-04-11 | Dsm N.V. | Photocurable resin composition and optical material |
| US20040059013A1 (en) * | 2000-01-14 | 2004-03-25 | Takayoshi Tanabe | Photocurable resin composition and optical parts |
| WO2004033511A1 (en) * | 2002-10-08 | 2004-04-22 | Dsm Ip Assets B.V. | Photocurable resin composition and optical material |
-
2005
- 2005-12-16 WO PCT/NL2005/000868 patent/WO2006068465A1/en active Application Filing
- 2005-12-23 TW TW094146153A patent/TW200634039A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10324726A (en) * | 1997-05-23 | 1998-12-08 | Nippon Kayaku Co Ltd | Resin composition for optical material and its hardened material |
| US20040059013A1 (en) * | 2000-01-14 | 2004-03-25 | Takayoshi Tanabe | Photocurable resin composition and optical parts |
| WO2002029448A2 (en) * | 2000-10-03 | 2002-04-11 | Dsm N.V. | Photocurable resin composition and optical material |
| WO2004033511A1 (en) * | 2002-10-08 | 2004-04-22 | Dsm Ip Assets B.V. | Photocurable resin composition and optical material |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 1999, no. 03 31 March 1999 (1999-03-31) * |
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| TW200634039A (en) | 2006-10-01 |
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