CN101805422B - Energy ray-curable resin composition and cured product for optical lens sheet - Google Patents
Energy ray-curable resin composition and cured product for optical lens sheet Download PDFInfo
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- CN101805422B CN101805422B CN2010101192246A CN201010119224A CN101805422B CN 101805422 B CN101805422 B CN 101805422B CN 2010101192246 A CN2010101192246 A CN 2010101192246A CN 201010119224 A CN201010119224 A CN 201010119224A CN 101805422 B CN101805422 B CN 101805422B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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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
Abstract
The invention relates to an energy ray-curable resin composition and cured product for an optical lens sheet. The invention provides a resin composition with the demolding performance, the mould reappearance, good fit on the base material, high refractive index, high glass transition temperature and low viscosity. The energy ray-curable resin composition for the optical lens sheet comprises a mono-acrylate monomer (A) with a phenylate group, a compound (B) representing by the general formula (1) and a photopolymerization initiator (C), in the formula (1), R1 is the same or different and represents hydrogen or C1 to C4 alkyl, R2 is the same or different and represents C1 to C4 alkyl, m and n are average number of repetitions and the sum of m and n is 0.4 to 12.
Description
Technical field
The present invention relates to optical lens energy ray curable resin composition and cured article thereof.More specifically, the present invention relates to be particularly suitable for resin combination and the cured article thereof of the lens classes such as Fresnel Lenses, biconvex lens, prismatic lens, microlens.
Background technology
In the past, above-mentioned lens were shaped by methods such as impact molding, castings (casting method).Therefore impact molding produces rate variance by a plurality of circulation manufacturings such as heating, pressurization, coolings.Casting is monomer to be injected mould carry out polymerization, so Production Time is long, and because the problem that needs a plurality of moulds thereby exist manufacturing cost to rise.In order to address these problems, about using ultra-violet solidified resin composition various schemes (patent documentation 1, patent documentation 2) have been proposed.
Obtained to a certain extent success by the method for making the middle optical lens that use such as transmission screen with ultraviolet-curing resin composition.But there is the poor problem of release property poor with the adaptation of substrate and that peel off from mould in the cured article of these existing resin combinations.If adaptation is poor, then the kind of spendable substrate is limited, is difficult to obtain required optics physical property.If release property is poor, then resin residue is on mould during the demoulding, and mould becomes and can not use.In addition, also there are the following problems: provide the good cured article of adaptation resin combination since with the driving fit of mould might as well, so easy variation of release property, on the other hand, the easy variation of resin combination adaptation that release property is good.Therefore, be desirable to provide the resin combination that can satisfy these two kinds of performances of release property of peeling off with the adaptation of substrate with from mould.
The lens class composition that uses in the optical lens etc. along with the in recent years high-precision refinement of image and the slimming of finished product etc., requires the high resin combination of specific refractory power.In addition, in order to be processed into finer shape or to process thinlyyer or be processed as continuously sheet or the film of web-like, the tendency of requirement low viscosity resin composition is arranged.In addition, the microtexture such as also require when batching lens survivable.In addition, because the thermal conductance of light source etc. causes that lens shape changes also is fatal, at this moment, require second-order transition temperature (Tg) height when using as goods are actual.
Wherein, proposed to have concurrently the resin combination of adaptation, two kinds of performances of release property in patent documentation 3, still, the viscosity that is used for being processed as fine shape more is not talkative fully; Disclose (methyl) acrylate of use dinaphthol as the liquid crystal material in patent documentation 4, still, purposes is limited to the liquid crystal material, for the clearly record of speciality of optics aspect.
No matter be which kind of situation, as all being difficult to have concurrently high refractive index, high Tg point, release property, adaptation and low viscosity with composition having high refractive index and have the lens class of using in the optical lens etc. of microtexture, thereby not yet obtain to satisfy the lens class composition of all characteristics.
Patent documentation 1: Japanese kokai publication sho 63-167301 communique
Patent documentation 2: Japanese kokai publication sho 63-199302 communique
Patent documentation 3: No. the 3209554th, Japanese Patent
Patent documentation 4: No. 2008/0090026 specification sheets of U.S. Patent Application Publication
Summary of the invention
The object of the present invention is to provide lens that be fit to make Fresnel Lenses, biconvex lens, prismatic lens, microlens etc. low viscosity resin composition and release property, mould circulation ratio, adaptation is good and the cured article of high refractive index.
The inventor has carried out research extensively and profoundly in order to address the above problem, and found that, ultra-violet solidified resin composition and cured article thereof with specific composition can address the above problem, and have finished the present invention.
That is, the present invention relates to the following.
(1) a kind of optical lens energy ray curable resin composition wherein, comprises:
Have the mono acrylic ester monomer (A) of phenylate base, compound (B) and the Photoepolymerizationinitiater initiater (C) of general formula (1) expression,
In the formula (1), R
1Identical or different, the alkyl of expression hydrogen atom or carbonatoms 1 to 4; R
2Identical or different, the alkyl of expression carbonatoms 1 to 4; M and n are average repeat number, m+n=0.4～12.
(2) above-mentioned (1) described resin combination, wherein, the mono acrylic ester monomer (A) that has a phenylate base is orthoxenol (many) oxyethyl group (methyl) acrylate, p-phenyl phenol (many) oxyethyl group (methyl) acrylate, orthoxenol epoxy (methyl) acrylate or p-phenyl phenol epoxy (methyl) acrylate.
(3) such as above-mentioned (1) or (2) described resin combination, wherein, compound (B) (methyl) acrylic compound (D) in addition that also comprises the expression of mono acrylic ester monomer (A) with phenylate base and general formula (1).
(4) such as each described resin combination in above-mentioned (1) to (3), wherein, (methyl) acrylic compound (D) is the compound with the structure that comprises the dihydroxyphenyl propane skeleton.
(5) such as each described resin combination in above-mentioned (1) to (4), wherein, be below the 3000mPas with the viscosity under 25 ℃ of E type viscometer determining.
(6) a kind of cured article obtains by each described resin combination in above-mentioned (1) to (5) is solidified, and the specific refractory power under 25 ℃ is more than 1.55.
(7) a kind of optical lens, the cured article described in its use above-mentioned (6).
The viscosity of resin combination of the present invention is low, the release property of its cured article, mould circulation ratio, good and specific refractory power is high with the adaptation of substrate.Therefore, be particularly suitable for the optical lens of Fresnel Lenses, biconvex lens, prismatic lens, microlens etc.
Embodiment
Resin combination of the present invention comprises the mono acrylic ester monomer (A) with phenylate base, compound (B) and the Photoepolymerizationinitiater initiater (C) of general formula (1) expression.
The mono acrylic ester monomer (A) that uses among the present invention, have the phenylate base is described.
As the mono acrylic ester monomer (A) with phenylate base, can enumerate: (methyl) vinylformic acid phenoxy ethyl, phenyl (many) oxyethyl group (methyl) acrylate, (methyl) vinylformic acid are to cumyl phenoxy ethyl, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid thiophenyl ethyl ester, (methyl) vinylformic acid-2-hydroxyl-3-phenoxy group propyl ester, phenylphenol (many) oxyethyl group (methyl) acrylate, phenylphenol epoxy (methyl) acrylate etc.Wherein, preferred phenylphenol (many) oxyethyl group (methyl) acrylate and phenylphenol epoxy (methyl) acrylate among the present invention, wherein, preferred orthoxenol (many) oxyethyl group (methyl) acrylate, p-phenyl phenol (many) oxyethyl group (methyl) acrylate, orthoxenol epoxy (methyl) acrylate and p-phenyl phenol epoxy (methyl) acrylate.
As phenylphenol (many) oxyethyl group (methyl) acrylate, the compound of the positive number of the repeat number average out to 1～3 of preferred oxyethyl group structure division can react to obtain with (methyl) vinylformic acid by making as the phenylphenol of raw material and the reaction product of oxyethane.Can use commercially available product (for example, as O-PP, P-PP, all can obtain from Sanko Co., Ltd.) as the orthoxenol of ortho position body with as the p-phenyl phenol of contraposition body in the phenylphenol.The reaction product of phenylphenol and oxyethane can obtain by known method, perhaps also can use commercially available product.By in the presence of the stoppers such as the esterifying catalysts such as tosic acid or sulfuric acid, Resorcinol or thiodiphenylamine, preferably in solvent based (for example, toluene, hexanaphthene, normal hexane, normal heptane etc.) existence under, the reaction product and the reaction of (methyl) vinylformic acid that preferably under 70～150 ℃, make phenylphenol and oxyethane, can obtain the many oxyethyl groups of phenylphenol (methyl) acrylate.(methyl) acrylic acid usage ratio is 1～5 mole, preferred 1.05～2 moles with respect to 1 mole of the reaction product of phenylphenol and oxyethane.Esterifying catalyst is 0.1～15 % by mole, preferred 1～6 % by mole with respect to (methyl) vinylformic acid that uses.
Phenylphenol epoxy (methyl) acrylate can by make the reaction of above-mentioned phenylphenol and epihalohydrin in the presence of alkali metal hydroxide, make its resultant of reaction Resins, epoxy and (methyl) vinylformic acid react to obtain again.
As this epihalohydrin, can use Epicholorohydrin, Alpha-Methyl Epicholorohydrin, γ-methyl epichlorohydrin, epibromohydrin etc., wherein the facile Epicholorohydrin of preferred industrial appearance.
The usage quantity of epihalohydrin is generally 2～20 moles with respect to 1 mole of phenylphenol, preferred 3～15 moles.
As this alkali metal hydroxide, can enumerate sodium hydroxide, potassium hydroxide etc., can use solid substance, also can use its aqueous solution.When using the aqueous solution, can adopt following method: when adding to the aqueous solution of this alkali metal hydroxide in the reaction system continuously, under reduced pressure or water and epihalohydrin are distillated, carry out again separatory except anhydrating, and epihalohydrin is turned back in the reaction system.The usage quantity of alkali metal hydroxide is generally 0.1～10.0 mole with respect to 1 mole of above-mentioned phenylphenol, and preferred 0.3～5.0 mole, more preferably 0.8～3.0 mole.
In order to promote reaction, preferably add the quaternary ammonium salts such as tetramethyl ammonium chloride, 4 bromide, trimethyl benzyl ammonia chloride as catalyzer.When using quaternary ammonium salt, its usage quantity is generally 0.1～20g with respect to 1 mole of above-mentioned phenylphenol, preferred 0.2～15g.
At this moment, carry out the aspect from reaction and consider, preferably add aprotic polar solvents such as the aliphatic alcohols such as methyl alcohol, ethanol, Virahol, dimethyl sulfone, methyl-sulphoxide, tetrahydrofuran (THF), dioxane etc. and react.
When using alcohols, its usage quantity is generally 1～50 quality %, preferred 2～30 quality % with respect to the usage quantity of epihalohydrin.In addition, when using aprotic polar solvent, be generally 3～100 quality %, preferred 5～80 quality % with respect to the usage quantity of epihalohydrin.
Temperature of reaction is generally 30～100 ℃, preferred 35～90 ℃.Reaction times is generally 0.2～10 hour, preferred 0.5～8 hour.In the presence of alkali metal hydroxide, with after the reaction solution washing of phenylphenol and epihalohydrin reaction or in the situation that do not wash, under the heating decompression, remove epihalohydrin etc.In addition, in order to obtain the few Resins, epoxy of hydrolyzable halogen, the Resins, epoxy that obtains can be dissolved in toluene, the mibk equal solvent, and the aqueous solution that adds the alkali metal hydroxides such as sodium hydroxide, potassium hydroxide reacts, thereby obtain the product of reliable closed loop.At this moment, the usage quantity of alkali metal hydroxide is generally 0.01～0.5 mole, preferred 0.05～0.3 mole with respect to 1 mole of the phenylphenol that uses.Temperature of reaction is generally 50～120 ℃, and the reaction times is generally 0.5～2 hour.
Reaction is removed the salt of generation after finishing by filtration, washing etc., distill desolventizing etc. again under the heating decompression, can obtain target Resins, epoxy thus.By the method take such method as representative, can obtain need not to carry out the Resins, epoxy that special purifying just can use.
Phenylphenol epoxy (methyl) acrylate is by obtaining described Resins, epoxy and the reaction of (methyl) vinylformic acid.With respect to 1 epoxy equivalent (weight) of described Resins, epoxy, make preferred 0.8～1.1 equivalent, more preferably (methyl) vinylformic acid reaction of 0.9～1.05 equivalent.
Reaction can be carried out under condition of no solvent, also can in the independent or mixed organic solvents of the solvent that does not have alcoholic extract hydroxyl group, carry out as required, such as: the ketones such as propyl alcohol, methylethylketone, hexalin; The arene such as benzene,toluene,xylene, tetramethyl-benzene; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dme, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether; The ester classes such as ethyl acetate, butylacetate, methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Trivalin SF acetic ester, propylene glycol monomethyl ether monoacetate, pentanedioic acid dialkyl, Succinic Acid dialkyl, hexanodioic acid dialkyl; The cyclic ester classes such as gamma-butyrolactone; The petroleum solvents such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha; And the various monomers that comprise mono acrylic ester monomer described later (C) and (methyl) acrylic compound (D), for example: acryloyl morpholine, the terminal acrylate compound of the ethylene oxide adduct of 2-phenylphenol (for example, the OPP-1 that Nippon Kayaku K. K makes, OPP-2), polyoxyethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the many oxyethyl groups three of TriMethylolPropane(TMP) (methyl) acrylate, the many propoxy-three of glycerine (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid DOPCP (for example, KAYARAD HX-220 of Nippon Kayaku K. K's manufacturing, HX-620 etc.), tetramethylolmethane four (methyl) acrylate, many (methyl) acrylate of the reaction product of Dipentaerythritol and 6-caprolactone, Dipentaerythritol many (methyl) acrylate etc.
During reaction, in order to promote to react preferred use catalyzer, the usage quantity of this catalyzer is 0.1～10 quality % with respect to reaction product when using catalyzer.The temperature of reaction of this moment is 60～150 ℃, and in addition, the reaction times is preferably 5～60 hours.As the catalyzer that uses, can enumerate such as triethylamine, benzyldimethylamine, triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.
In addition, can use the thermopolymerization hold back agent, as this thermopolymerization hold back agent, for example can enumerate: hydroquinone monomethyl ether, 2-methyl hydroquinone, Resorcinol, 2,6-ditertbutylparacresol, diphenylpicrylhydrazine, diphenylamine etc., when using the thermopolymerization hold back agent, preferably take with respect to reactant as approximately 0.1 quality %～approximately the amount of 10 quality % is used.Suitably sampling in the reaction reaches moment below the 5mgKOH/g, below the preferred 3mgKOH/g as terminal point with the acid number of sample.
Below, compound (B) that use in the resin combination of the present invention, general formula (1) expression is described.
Compound of the present invention (B) can be by making 1,1 '-dinaphthol and oxirane or alkylene carbonate reaction, then in the presence of acid catalyst and (methyl) vinylformic acid carry out dehydration condensation and obtain.Among the present invention, as 1,1 '-dinaphthol, preferred (RS)-1 of using, 1 '-union-2-naphthol can be from S﹠amp; R CHIRAL CHEMICAL company etc. obtains.1, in the reaction of 1 '-dinaphthol and oxirane, with respect to 1 mole 1,1 '-dinaphthol makes 0.5～24 mole oxirane reaction.1, in the reaction of 1 '-dinaphthol and alkylene carbonate, with respect to 1 mole 1,1 '-dinaphthol makes 2～5 moles alkylene carbonate reaction.Oxirane or alkylene carbonate can be used alone, and also can two or more mixing use.
As the concrete example of oxirane, can enumerate: (carbonatoms 1～4) oxiranes such as oxyethane, propylene oxide, butylene oxide ring.In addition, as the concrete example of alkylene carbonate, can enumerate: carbonic acid (carbonatoms 1～4) alkylene carbonate such as ethylene carbonate, Texacar PC, butylene carbonate.
1, the reaction of 1 '-dinaphthol and oxirane or alkylene carbonate is under the basic catalysts such as sodium hydroxide, potassium hydroxide, carry out under the condition of 1～48 hour reaction times, 90～200 ℃ of temperature of reaction.1, in the reaction of 1 '-dinaphthol and oxirane, with respect to 100 quality % reaction mixtures, use the basic catalyst of 0.01～5 quality %.1, in the reaction of 1 '-dinaphthol and alkylene carbonate, with respect to 1 mole 1,1 '-dinaphthol uses 0.01～0.5 mole basic catalyst.
1, in the reaction product of 1 '-dinaphthol and oxirane or alkylene carbonate and (methyl) acrylic acid dehydration condensation, with respect to 1 mole 1,1 '-dinaphthol uses (methyl) vinylformic acid of 0.1～10 mole.As the reaction solvent in the dehydration condensation, can use the azeotropic solvent that the water distillation that generates in the reaction can be removed.At this, so-called azeotropic solvent refers to have 60～130 ℃ boiling point, can be easily with moisture from solvent, particularly preferably use a kind of of the non-reacted organic solvents such as benzene, toluene, normal hexane, normal heptane, hexanaphthene or be use mixing two or more.Its usage quantity is arbitrarily, is 10～70 quality % with respect to reaction mixture preferably.
The reaction times of dehydration condensation can be in 1～24 hour scope, and temperature of reaction can be considered from the viewpoint of Reaction time shorten and inhibition in 60～150 ℃ scope, preferably carried out under 75～120 ℃.
In commercially available product (methyl) vinylformic acid as the raw material use, usually add the stoppers such as p methoxy phenol, can again add stopper during reaction.As the example of such stopper, can enumerate: Resorcinol, p methoxy phenol, 2,4 dimethyl 6 tert butyl phenol, 3-hydroxythiophenol, para benzoquinone, 2,5-dihydroxyl para benzoquinone, thiodiphenylamine etc.Its usage quantity is 0.01～1 quality % with respect to reaction mixture.
The acid catalyst that uses in the dehydration condensation, can select arbitrarily from the known acid catalysts such as sulfuric acid, methylsulfonic acid, trifluoromethanesulfonic acid, tosic acid, its usage quantity is 0.01～10 mole, preferred 1～5 % by mole with respect to 1 mole of (methyl) vinylformic acid.
The compound that uses in the resin combination of the present invention (B), if consider that specific refractory power reaches and the consistency of other composition, preferably with respect to 1 mole 1,1 '-dinaphthol makes 0.5～4 mole oxirane reaction and the compound that obtains or with respect to 1 mole 1, and 1 '-dinaphthol makes 2～4 moles alkylene carbonate reaction and the compound that obtains.As oxirane, then can be any one if methylene radical is 1～4 oxirane, optimization ethylene oxide or propylene oxide.As alkylene carbonate, then can be any one if methylene radical is 1～4 alkylene carbonate, preferred ethylene carbonate or Texacar PC.
In addition, except the compound (B) of the mono acrylic ester monomer (A) with phenylate base enumerated previously and general formula (1) expression, the hardness of the viscosity of the resin combination of the present invention that consideration obtains, adaptation, second-order transition temperature (Tg), cured article etc. can be used separately or composition (A), composition (B) (methyl) acrylic compound (D) are in addition used in two or more mixing.As this (methyl) acrylic compound (D), can enumerate (methyl) acrylate monomer or (methyl) origoester acrylate.
As (methyl) acrylate monomer, can enumerate above multifunctional (methyl) acrylate monomer of simple function (methyl) acrylate monomer, difunctionality (methyl) acrylate monomer, trifunctional etc.
As simple function (methyl) acrylate monomer, for example can enumerate: acryloyl morpholine, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxyl butyl ester, hexanaphthene-Isosorbide-5-Nitrae-dimethanol list (methyl) acrylate, (methyl) tetrahydrofurfuryl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid tribromophenoxy ethyl ester, (methyl) vinylformic acid dicyclo pentyl ester (dicyclopentanyl (meth) acrylate), (methyl) vinylformic acid double cyclopentenyl ester (dicyclopentenyl (meth) acrylate)), (methyl) vinylformic acid double cyclopentenyl oxygen ethyl ester (dicyclopentenyl oxyethyl (meth) acrylate)) etc.
As difunctionality (methyl) acrylate monomer, can enumerate: 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, tristane dimethanol two (methyl) acrylate, the many oxyethyl groups two of dihydroxyphenyl propane (methyl) acrylate, the many propoxy-two of dihydroxyphenyl propane (methyl) acrylate, the many oxyethyl groups two of Bisphenol F (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, two (methyl) acrylate of the 6-caprolactone affixture of hydroxypivalic acid DOPCP (for example, KAYARAD HX-220 of Nippon Kayaku K. K's manufacturing, HX-620 etc.).
As multifunctional (methyl) acrylate monomer more than the trifunctional, can enumerate: isocyanuric acid three (acrylyl oxy-ethyl) ester, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, tripentaerythritol six (methyl) acrylate, tripentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, the many oxyethyl groups three of TriMethylolPropane(TMP) (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate etc.
As (methyl) origoester acrylate, can enumerate: carbamate (methyl) acrylate, epoxy (methyl) acrylate, polyester (methyl) acrylate etc.
As carbamate (methyl) acrylate, for example can enumerate: make diol compound (for example, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 6-hexylene glycol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, the 3-methyl isophthalic acid, the 5-pentanediol, 2,4-diethyl-1, the 5-pentanediol, 2-butyl-2-ethyl-1, ammediol, hexanaphthene-1, the 4-dimethanol, polyoxyethylene glycol, polypropylene glycol, many oxyethyl groups of dihydroxyphenyl propane glycol, many propoxy-of dihydroxyphenyl propane glycol etc.) or these diol compounds and diprotic acid or its acid anhydrides (for example, Succinic Acid, hexanodioic acid, nonane diacid, dimeracid, m-phthalic acid, terephthalic acid, phthalic acid or their acid anhydrides) the reaction product polyester glycol and organic multiple isocyanate (for example, 1,4-fourth vulcabond, 1, hexamethylene-diisocyanate, 2,2,4-trimethylammonium-hexamethylene diisocyanate, 2,4, the chain stable hydrocarbon isocyanic ester such as 4-trimethylammonium-hexamethylene diisocyanate; The cyclic saturated hydrocarbon isocyanic ester such as isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methane diisocyanate, methylene-bis (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate; 2,4-cresylene vulcabond, 1,3-xylylene diisocyanate, PPDI, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond, 6-sec.-propyl-1,3-phenylene diisocyanate, 1, the aromatic polyisocyanates such as 5-naphthalene diisocyanate) reaction, the reaction product that then obtains with hydroxyl (methyl) acrylate addition.In addition, can also enumerate described organic multiple isocyanate and hydroxyl (methyl) acrylate reactions and compound of obtaining etc.
As epoxy (methyl) acrylate, can enumerate: the epoxy resins such as the terminal glycidyl group ether of the propylene oxide adduct of bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic resin varnish type epoxy resin, dihydroxyphenyl propane, fluorenes Resins, epoxy and (methyl) acrylic acid reaction product etc.
As polyester (methyl) acrylate, can enumerate such as: the reaction product polyester glycol of above-mentioned diol compound and above-mentioned diprotic acid or its acid anhydrides and (methyl) acrylic acid reaction product etc.
Wherein, as (methyl) acrylic compound (D) that can in resin combination of the present invention, use, if the compound of considering specific refractory power then preferably having the structure that comprises the dihydroxyphenyl propane skeleton, for example, the many oxyethyl groups two of dihydroxyphenyl propane (methyl) acrylate, (methyl) acrylate monomers such as the many propoxy-two of dihydroxyphenyl propane (methyl) acrylate, carbamate (methyl) origoester acrylate (many oxyethyl groups of dihydroxyphenyl propane glycol with dihydroxyphenyl propane skeleton, the diol compounds such as many propoxy-of dihydroxyphenyl propane glycol, the perhaps reaction product polyester glycol of these diol compounds and diprotic acid or its acid anhydrides, with organic multiple isocyanate and hydroxyl (methyl) acrylate reactions and the compound that obtains), epoxy (methyl) origoester acrylate (bisphenol A type epoxy resin with dihydroxyphenyl propane skeleton, the epoxy resin such as the terminal glycidyl group ether of the propylene oxide adduct of dihydroxyphenyl propane and (methyl) acrylic acid reaction product etc.) be fit to.
In addition, if the adaptation of consideration cured article and viscosity etc., as (methyl) acrylic compound (D), simple function or difunctionality (methyl) acrylate monomer is fit to, wherein, preferred acryloyl morpholine, (methyl) tetrahydrofurfuryl acrylate, (methyl) vinylformic acid phenoxy ethyl, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclo pentyl ester, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid double cyclopentenyl ethyl ester etc.
In addition, if consider the second-order transition temperature (Tg) of cured article, as (methyl) acrylic compound (D), above (methyl) acrylate monomers of trifunctional such as preferred isocyanuric acid three (acrylyl oxy-ethyl) ester, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, trimethylolpropane tris (methyl) acrylate.
As Photoepolymerizationinitiater initiater contained in the resin combination of the present invention (C), can enumerate: the bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, bitter almond oil camphor propyl ether, benzoin iso-propylether; Methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinyl propane-1-ketone, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone] etc. acetophenones; The Anthraquinones such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, ITX, CTX; The ketal classes such as methyl phenyl ketone dimethyl ketal, dibenzoyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 4, the benzophenones such as 4 '-dimethylamino benzophenone; 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,4,6-Three methyl Benzene formyl)-phenylphosphine oxide, the phenylbenzene-phosphine oxide classes such as (2,4,6-Three methyl Benzene formyl) phosphine oxide; Deng.Acetophenones be can preferably enumerate, 2-hydroxy-2-methyl phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone further preferably enumerated.In addition, in the resin combination of the present invention, Photoepolymerizationinitiater initiater (C) can use separately, also can multiple mixing use, and preferably uses 2,4,6-Three methyl Benzene formyl diphenyl phosphine oxide, two (2,4,6-Three methyl Benzene formyl)-phenylphosphine oxide, phenylbenzene-(2,4,6-Three methyl Benzene formyl) at least a in the phosphine oxide class such as phosphine oxide.
The usage ratio of each composition of resin combination of the present invention can consider that required specific refractory power, second-order transition temperature, viscosity and adaptation etc. are next definite, with composition (A)+composition (B)+composition (D) when being set as 100 mass parts, the content of composition (A)+composition (B) is 50～100 mass parts, 70～100 mass parts particularly preferably, therefore, the content of composition (D) is less than 50 mass parts, particularly preferably less than 30 mass parts.In addition, when the total amount of composition (A)+composition (B) was set as 100 mass parts, the content of composition (A) was 10～95 mass parts wherein, particularly preferably 20～90 mass parts.Composition (C) preferably uses 0.1～10 mass parts, particularly preferably 0.3～5 mass parts with respect to total amount 100 mass parts of composition (A)+composition (B)+composition (D).
In the energy ray curable resin composition of the present invention, except aforementioned composition, conveniences when operating in order to improve etc. can according to circumstances make up and contain releasing agent, defoamer, flow agent, photostabilizer, antioxidant, stopper, antistatic agent, UV light absorber etc.In addition, also can add as required the polymer class such as acrylic polymers, polyester elastomer, urethane and nitrile rubber, inorganic or organic light diffusion filler etc.Also can add solvent, but preferably not add solvent.
Resin combination of the present invention can be by preparing each composition mixed dissolution according to conventional methods.For example, can be by each composition being dropped in the round-bottomed flask with whipping appts and thermometer, and stir at 40～80 ℃ and to obtain in 0.5～6 hour.
The viscosity of resin combination of the present invention, as viscosity that be fit to make the optical lens class, preferably use E type viscometer (TV-200: the viscosity of eastern machine industry company system) measuring 25 ℃ lower as 3000mPas below.
Available cured article is also contained among the present invention by according to conventional methods resin combination irradiation ultraviolet radiation homenergic ray of the present invention being made its curing.This cured article can followingly obtain: resin combination of the present invention is applied to has for example Fresnel Lenses, biconvex lens, on the pressing mold of the shape of prismatic lens etc. and the layer of this resin combination is set, gluing backboard as the hard transparent substrate (for example on this layer, comprise polymethacrylate resin, polycarbonate resin, polystyrene resin, substrate or the film of the blend of vibrin or these polymkeric substance etc.), then, utilize the irradiation ultraviolet radiation such as high voltage mercury lamp that this resin combination is solidified from this hard transparent substrate-side after, cured article is peeled off from this pressing mold.In addition, as the application of aforesaid method, also can be undertaken by the processing of continous way.
The optical lens of the optical lens part of the Fresnel Lenses of can obtain like this being formed with specific refractory power (25 ℃) and be more than 1.55, release property, mould circulation ratio, adaptation and photostabilization are good, biconvex lens, prismatic lens, microlens etc., these are also contained among the present invention.The ア タ of Co., Ltd. go system) in addition, specific refractory power can be passed through Abbe refractomecer (DR-M2: the mensuration such as.
Resin combination of the present invention can be used for optical lens as mentioned above.As the purposes beyond the optical lens, can enumerate various coating agents, tackiness agent etc.
Embodiment
Below, illustrate in greater detail the present invention by embodiment.In addition, the present invention is not subjected to any restriction of following examples.
Synthesizing of compound (B)
Synthesis example 1
With 286.3g (1.0mol) (RS)-1,1 '-union-2-naphthol, 264.2g (3.0mol) ethylene carbonate, 41.5g (0.3mol) salt of wormwood and 2000ml toluene join have whipping appts, in the flask of return line and thermometer, and 110 ℃ of reactions 12 hours.
After the reaction, to the gained reaction solution wash, with the 1%NaOH solution washing, then wash until washing water are neutral.Use the solvent distillation in the solution after rotatory evaporator under reduced pressure will be washed to remove, obtain 300.0g (RS)-1, the oxyethane 2mol reaction product of 1 '-union-2-naphthol.
Then, with 187.2g (0.5mol) (RS)-1, the oxyethane 2mol reaction product of 1 '-union-2-naphthol, 86.5g (2.4mol) vinylformic acid, 0.95g tosic acid, 0.87g Resorcinol, 917.4g toluene, 393.2g hexanaphthene join have whipping appts, in the flask of return line, thermometer and water trap, when under 95～105 ℃ temperature of reaction, reacting, water and solvent component distillation that reaction generates are removed.After the reaction, with in the 25%NaOH aqueous solution and after, with 200g 15 quality % salt solutions washing three times.The underpressure distillation desolventizing obtains the resultant 337.8g shown in the following structural formula of faint yellow solid form.
The physical property of compound (B) is as follows.
Liquid refractivity (D line, 25 ℃) 1.62
1H-NMR(CDCl
3、300MHz)、ppm：
4.00-4.30ppm＝8H，5.60-5.90ppm＝4H，6.05-6.15ppm＝2H，7.05-7.50ppm＝8H，7.80-8.00ppm＝4H
Synthesizing of compound (D)
Synthesis example 2
139.3 parts of 2,4 toluene diisocyanates, 0.05 part of di-n-butyltin dilaurate and 0.16 part of p methoxy phenol are joined in the drying receptacle, be warming up to 40 ℃ and stirring.With 1 hour to wherein dripping 185.6 parts of 2-Hydroxy ethyl acrylates, confirm simultaneously the heat production state, 80 ℃ the reaction 1～2 hour.Reacted isocyanate value is below 0.1, and expression reaction basal ration is finished.
Obtain resin combination of the present invention and cured article according to the composition shown in following examples (numeric representation mass parts).In addition, as described below about evaluation method and the judgement criteria of resin combination and cured film.
(1) viscosity: use E type viscometer (TV-200: Toki Sangyo Co., Ltd.'s system), under 25 ℃, measure.
(2) release property: the resin that expression is solidified is the difficulty the during demoulding from the mould.
Zero: the good demoulding from the mould
△: the demoulding is slightly had any problem or is peeled off sound during the demoulding
*: on demoulding difficulty or the mould residue is arranged
(3) mould circulation ratio: observe the surface shape of the uv curing resin layer that solidifies and the surface shape of mould.
Zero: circulation ratio is good
*: circulation ratio is bad
(4) adaptation:
With resin combination be applied on the base material to thickness be about 50 μ m, then use high voltage mercury lamp (80W/cm, ozone free) to carry out 1000mJ/cm
2Irradiation, the test piece of make solidifying is carried out the adaptation evaluation according to JIS K5600-5-6.
Evaluation result be with 0～2 as zero, with 3～5 as *.
(5) specific refractory power (25 ℃): use Abbe refractomecer (DR-M2: the specific refractory power (25 ℃) of the ultraviolet curing resin layer after the ア タ of Co., Ltd. go system) mensuration is solidified.
(6) second-order transition temperature (Tg): use determination of viscoelasticity system (DMS-6000: Seiko Instruments Inc's system), at the Tg point of measuring the uv curing resin layer after solidifying under stretch mode, the frequency 1Hz.
Embodiment 1
Will be as 31 parts of orthoxenols, the one ethoxy propylene acid esters of composition (A), 20 parts of compounds that synthesis example 1 obtains as composition (B), 3 parts of 1-hydroxycyclohexylphenylketones as composition (C), 0.1 part phenylbenzene-(2,4,6-Three methyl Benzene formyl) phosphine oxide and as 20 parts of KAYARAD R-551 (Japanese chemical drug systems of composition (D), many oxyethyl groups of dihydroxyphenyl propane diacrylate), 4 parts of KAYARAD R-115 (Japanese chemical drug systems, bisphenol A epoxy acrylate), 18 part of three (2-acrylyl oxy-ethyl) isocyanic ester and 7 parts of acryloyl morpholines are heated to 60 ℃ and mixing, obtain resin combination of the present invention.The viscosity of this resin combination is 904mPas.In addition, by with high voltage mercury lamp (80w/cm, ozone free) this resin combination being carried out 600mJ/cm
2Irradiation make its curing and the specific refractory power (25 ℃) of the ultraviolet curing resin layer of the thickness 200 μ m that obtain is 1.587, second-order transition temperature (Tg) is 94 ℃.
And then, this resin combination is applied to make thickness on the prismatic lens mould be 50 μ m, gluing easy to be gluing PET film as base material (it is thick that コ ス モ シ ヤ イ Application A4300,100 μ m spin in Japan) is just used high voltage mercury lamp radiation 1000mJ/cm more from it thereon
2The ultraviolet ray of irradiation dose is peeled off after it is solidified, and obtains prismatic lens sheet of the present invention.
Evaluation result
Release property: zero; Mould circulation ratio: zero; Adaptation: zero
Embodiment 2
Use 52 parts of orthoxenol one ethoxy propylene acid esters as composition (A), use 3 parts of 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone as composition (C), use compound, 13 parts of acryloyl morpholines and 5 parts of tetrahydrofurfuryl acrylates that 10 parts of synthesis examples 2 obtain as composition (D), obtain similarly to Example 1 in addition resin combination of the present invention.The viscosity of this resin combination is 195mPas.In addition, operate similarly to Example 1 and the specific refractory power (25 ℃) of the resin layer that obtains is 1.597, second-order transition temperature (Tg) is 69 ℃.
Use the resin combination of gained to operate similarly to Example 1, obtain prismatic lens sheet of the present invention.
Evaluation result
Release property: zero; Mould circulation ratio: zero; Adaptation: zero
Comparative example 1
Embodiment 1 according to patent documentation 1 (Japanese kokai publication sho 63-167301), with 70 parts of ア ロ ニ Star Network ス M315 (isocyanuric acid three (2-acrylyl oxy-ethyl) ester), 30 parts of tetrahydrofurfuryl acrylates, be heated to 60 ℃ and mix as 3 parts of 1-(4-isopropyl phenyl) of Photoepolymerizationinitiater initiater-2-hydroxy-2-methyl-2-propane-1-ketone, obtain the relatively resin combination of usefulness.The viscosity of this resin combination is 134mPas.In addition, operate similarly to Example 1 and the specific refractory power (25 ℃) of the resin layer that obtains is 1.52.
Can find out from this result, the refractive index ratio of the composition of comparative example 1 composition of the present invention is low, is not suitable for making lens class of the present invention.
Comparative example 2
Embodiment 1 according to patent documentation 3 (No. the 3209554th, Japanese Patent), urethane acrylate (the polyester glycol of neopentyl glycol and hexanodioic acid of the synthesis example 1 of the synthetic document, ethylene glycol, the reaction product of cresylene vulcabond and 2-Hydroxy ethyl acrylate) and the compound of document synthesis example 3 (orthoxenol diethoxy propene acid esters), with 30 parts of above-mentioned urethane acrylates, 15 parts of above-mentioned orthoxenol diethoxy propene acid esters, 45 parts of KAYARAD R-551,10 parts of tribromophenyl acrylates and 3 parts of イ Le ガ キ ュ ア one (1-hydroxycyclohexylphenylketones) are heated to 60 ℃ and mixing, obtain the relatively resin combination of usefulness.The viscosity of this resin combination is 4420mPas.In addition, operate similarly to Example 1 and the specific refractory power (25 ℃) of the resin layer that obtains is 1.574.
Can be found out that by this result the viscosity ratio of the composition of comparative example 2 combination object height of the present invention is not suitable for the continuous processing of sheet or the film of fine processing or web-like.
Can find out from embodiment 1,2, comparative example 1,2 evaluation result, resin combination viscosity of the present invention with specific composition is low, release property, mould circulation ratio and good to the adaptation of base material, and the specific refractory power of its cured article is high and second-order transition temperature (Tg) height.Therefore, be suitable for having the optical lens of microtexture, such as Fresnel Lenses, biconvex lens, prismatic lens, microlens etc.The manufacturing that is particularly suitable for to carry out the purposes of microfabrication or comprises the operation that to process continuously.
Industrial applicability
Ultra-violet solidified resin composition of the present invention and cured article thereof mainly are particularly suitable for the optical lens of Fresnel Lenses, biconvex lens, prismatic lens, microlens etc.
Claims (7)
1. optical lens energy ray curable resin composition wherein, comprises:
Have the mono acrylic ester monomer (A) of phenylate base, compound (B) and the Photoepolymerizationinitiater initiater (C) of general formula (1) expression,
In the formula (1), R
1Identical or different, the alkyl of expression hydrogen atom or carbonatoms 1 to 4; R
2Identical or different, the alkyl of expression carbonatoms 1 to 4; M and n are average repeat number, m+n=0.4～12.
2. resin combination as claimed in claim 1, wherein, the mono acrylic ester monomer (A) that has a phenylate base is orthoxenol one oxyethyl group (methyl) acrylate, the many oxyethyl groups of orthoxenol (methyl) acrylate, p-phenyl phenol one oxyethyl group (methyl) acrylate, the many oxyethyl groups of p-phenyl phenol (methyl) acrylate, orthoxenol epoxy (methyl) acrylate or p-phenyl phenol epoxy (methyl) acrylate.
3. resin combination as claimed in claim 1 or 2 wherein, also comprises mono acrylic ester monomer (A) with phenylate base and compound (B) (methyl) acrylic compound (D) in addition of general formula (1) expression.
4. such as each described resin combination in the claims 1 to 3, wherein, (methyl) acrylic compound (D) is the compound with the structure that comprises the dihydroxyphenyl propane skeleton.
5. such as each described resin combination in the claim 1 to 4, wherein, be below the 3000mPas with the viscosity under 25 ℃ of E type viscometer determining.
6. cured article obtains by each described resin combination in the claim 1 to 5 is solidified, and the specific refractory power under 25 ℃ is more than 1.55.
7. optical lens, its right to use requires 6 described cured articles.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009034748A JP5219084B2 (en) | 2009-02-18 | 2009-02-18 | Energy ray curable resin composition for optical lens sheet and cured product thereof |
| JP2009-034748 | 2009-02-18 |
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| CN101805422A CN101805422A (en) | 2010-08-18 |
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| JP (1) | JP5219084B2 (en) |
| KR (1) | KR101558338B1 (en) |
| CN (1) | CN101805422B (en) |
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| JP2013028662A (en) * | 2011-07-27 | 2013-02-07 | Nippon Kayaku Co Ltd | Energy ray-curable resin composition for optical lens sheet and cured product using the same |
| JP2013166900A (en) * | 2012-02-17 | 2013-08-29 | Nippon Kayaku Co Ltd | Energy beam curable resin composition for hard coat film, and hard coat film (1) |
| JP2013167837A (en) * | 2012-02-17 | 2013-08-29 | Nippon Kayaku Co Ltd | Energy beam curable resin composition for hard coat film, and hard coat film (2) |
| JP6137172B2 (en) * | 2012-04-03 | 2017-05-31 | 東亞合成株式会社 | Active energy ray-curable composition, metal substrate having cured film, and method for producing the same |
| JP6057409B2 (en) * | 2012-04-25 | 2017-01-11 | 日本化薬株式会社 | Energy ray curable resin composition for optical lens sheet and cured product thereof (1) |
| JP5974784B2 (en) * | 2012-09-28 | 2016-08-23 | Jnc株式会社 | Inkjet ink |
| JP6083901B2 (en) * | 2013-05-24 | 2017-02-22 | 田岡化学工業株式会社 | Method for producing binaphthalene compound |
| JP6083900B2 (en) * | 2013-05-24 | 2017-02-22 | 田岡化学工業株式会社 | Method for producing binaphthalene compound |
| CN105579488B (en) * | 2013-09-26 | 2017-07-21 | 田冈化学工业株式会社 | Epoxy resin with dinaphthalene skeleton |
| CN103553971A (en) * | 2013-10-25 | 2014-02-05 | 张家港威迪森化学有限公司 | Preparation method for urethane acrylate |
| JP6535002B2 (en) * | 2014-07-17 | 2019-06-26 | 日本化薬株式会社 | Liquid crystal sealing agent and liquid crystal display cell using the same |
| TWI558541B (en) * | 2015-04-02 | 2016-11-21 | 長興材料工業股份有限公司 | Photocurable lens and method of manufacturing the same |
| WO2018051713A1 (en) * | 2016-09-15 | 2018-03-22 | 富士フイルム株式会社 | Curable composition, cured material, optical member, lens, and compound |
| JP6635999B2 (en) * | 2017-10-13 | 2020-01-29 | 株式会社ダイセル | Method for producing potassium salt, and potassium salt |
| EP4105250A4 (en) * | 2020-02-10 | 2024-02-28 | Kuraray Noritake Dental Inc | Resin composition for stereolithography |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1454933A (en) * | 2003-04-01 | 2003-11-12 | 四川大学 | Photocurable resin composition |
| WO2008105455A1 (en) * | 2007-02-28 | 2008-09-04 | Nippon Kayaku Kabushiki Kaisha | Energy ray-curable resin composition for optical lens sheet and cured product thereof |
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| JPS5986615A (en) * | 1982-11-11 | 1984-05-18 | Showa Denko Kk | Polymerizable composition |
| JP2807315B2 (en) * | 1990-06-28 | 1998-10-08 | 日本化薬株式会社 | (Meth) acrylic acid ester, resin composition containing the same, and cured product thereof |
| JP3209554B2 (en) * | 1991-12-19 | 2001-09-17 | 日本化薬株式会社 | Resin composition, ultraviolet curable resin composition for transmission screen and cured product thereof |
| JPH09272707A (en) * | 1996-04-04 | 1997-10-21 | Toagosei Co Ltd | Actinic-radiation-curing (meth)acrylate composition |
| WO2002033447A1 (en) * | 2000-10-13 | 2002-04-25 | Nof Corporation | Composition for optical material, optical material, and plastic lens |
| JP4659288B2 (en) * | 2001-07-19 | 2011-03-30 | 独立行政法人産業技術総合研究所 | Composition for hologram recording material, hologram recording medium and method for producing the same |
| JP4802479B2 (en) * | 2004-02-18 | 2011-10-26 | Ｊｎｃ株式会社 | Polymerizable binaphthalene derivative |
| JP2005283632A (en) * | 2004-03-26 | 2005-10-13 | Fuji Photo Film Co Ltd | Polymerizable composition and negative image recording material |
| JP4433300B2 (en) * | 2005-01-05 | 2010-03-17 | 日本化薬株式会社 | Photosensitive resin composition and film having cured film thereof |
| JP5017938B2 (en) * | 2006-06-22 | 2012-09-05 | 川崎化成工業株式会社 | Photopolymerization sensitizer comprising bis (2- (meth) acryloxyalkoxy) naphthalene compound as an active ingredient, and use thereof |
| JP2008201972A (en) * | 2007-02-22 | 2008-09-04 | Kyocera Chemical Corp | Highly refractive material and optical transmission article using the same |
| KR101635801B1 (en) | 2007-04-27 | 2016-07-04 | 니폰 가야꾸 가부시끼가이샤 | (meth)acrylate compound, resin composition containing the same, cured product of the resin composition and energy ray-curable resin composition for optical lens sheet and cured product thereof |
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- 2010-02-09 TW TW099103903A patent/TWI454492B/en not_active IP Right Cessation
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| CN1454933A (en) * | 2003-04-01 | 2003-11-12 | 四川大学 | Photocurable resin composition |
| WO2008105455A1 (en) * | 2007-02-28 | 2008-09-04 | Nippon Kayaku Kabushiki Kaisha | Energy ray-curable resin composition for optical lens sheet and cured product thereof |
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| KR20100094369A (en) | 2010-08-26 |
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| KR101558338B1 (en) | 2015-10-07 |
| TW201035129A (en) | 2010-10-01 |
| JP5219084B2 (en) | 2013-06-26 |
| JP2010189534A (en) | 2010-09-02 |
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