WO2012020659A1 - Curable composition and article produced by curing same - Google Patents
Curable composition and article produced by curing same Download PDFInfo
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- WO2012020659A1 WO2012020659A1 PCT/JP2011/067596 JP2011067596W WO2012020659A1 WO 2012020659 A1 WO2012020659 A1 WO 2012020659A1 JP 2011067596 W JP2011067596 W JP 2011067596W WO 2012020659 A1 WO2012020659 A1 WO 2012020659A1
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- curable composition
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- cured resin
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- 0 C*(C(C)(C)OC(*)(CCCC1)CC1C1(C(*)(CCC2)CCCC2(*)O*OC*(C(*)=C)=O)c2ccccc2-c2ccccc12)OC(C(*)=C)=O Chemical compound C*(C(C)(C)OC(*)(CCCC1)CC1C1(C(*)(CCC2)CCCC2(*)O*OC*(C(*)=C)=O)c2ccccc2-c2ccccc12)OC(C(*)=C)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
-
- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
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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
- C08L33/062—Copolymers with monomers not covered by C08L33/06
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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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2312/00—Crosslinking
- C08L2312/02—Crosslinking with dienes
Definitions
- the present invention relates to a curable composition, a cured product thereof, and an optical member. More specifically, a curable composition that has a low viscosity before being cured and can be rapidly cured by heating to form a cured product having excellent optical properties and environmental resistance, and the curable composition
- the present invention relates to a cured resin obtained by curing and an optical member such as a lens made of the cured resin.
- Curable resin compositions are used as plastic materials in machine part materials, electrical / electronic parts materials, automobile parts materials, civil engineering and building materials, molding materials, paints, adhesives, sealing materials, etc. It is also attracting attention as a material for optical members.
- a curable composition for forming a low Abbe number lens As a curable composition for forming a low Abbe number lens, a curable composition mainly containing a (meth) acrylic acid ester having a fluorene ring is known (Patent Document 1). However, this curable composition cannot form a lens having a sufficiently low Abbe number, and it cannot be said that the heat resistance is sufficient, and when exposed to high temperatures, the shape changes or the light transmittance decreases significantly. It was a problem to do.
- Patent Document 2 discloses a (meth) acrylic acid ester having a fluorene ring to a naphthalene ring, an anthracene ring, Or the method of improving fluidity
- (meth) acrylates having a naphthalene ring, anthracene ring, or anthrone ring are not so low in viscosity and need to be added in a large amount in order to ensure appropriate fluidity. For this reason, adding an amount capable of sufficiently securing fluidity impairs optical properties, and it is difficult to combine fluidity and optical properties.
- the press molding method frequently used for thermoplastic resins and the like requires pretreatment such as pre-curing when molding a curable composition, and general resins are molding methods with excellent productivity.
- a method for forming a member that requires high heat resistance it has become a rather complicated method.
- Non-Patent Document 1 a method of adding an antioxidant is known.
- the antioxidant includes a radical scavenger that traps and invalidates the generated radicals, and a peroxide decomposer that decomposes the generated peroxide into an inactive substance and suppresses the generation of new radicals.
- radical scavengers hindered phenol compounds, hindered amine compounds, and peroxide decomposers are mainly used phosphorus compounds (Patent Document 3).
- the radical scavenger has an action of inhibiting radical polymerization, if a sufficient amount is added to exert the yellowing suppression effect, the curing of the curable composition itself does not proceed, and the resulting cured resin There was a problem that toughness decreased.
- Phosphorus compounds have a small effect on suppressing yellowing, and it is difficult to sufficiently suppress yellowing under high temperature conditions (for example, about 260 ° C.) such as soldering by a reflow method. When used as a material for members, the yellowing suppression effect was quite insufficient. Therefore, for example, most camera-equipped mobile phones are manufactured through a process of connecting a separately manufactured camera module with a connector after a soldering process (mounting process) by a reflow method, and the manufacturing process becomes complicated. It was.
- the object of the present invention is low viscosity before curing, cures quickly by heating, exhibits a low Abbe number of 30 or less, is excellent in transparency and heat resistance, and is soldered by a reflow method.
- a curable composition capable of forming a curable resin that does not easily yellow even under high temperature conditions such as attaching, a curable resin obtained by curing the curable composition, and an optical member made of the curable resin. There is.
- the present inventors have two (meth) acryloyloxy groups in the molecule that are extremely high in viscosity but excellent in optical properties and heat resistance, and When a specific amount of a compound having at least one vinyl group or (meth) acryloyloxy group in the molecule and not having a fluorene ring is added to the (meth) acrylic acid ester having a fluorene ring, the optical properties are maintained. It has been found that the fluidity can be improved by significantly reducing the viscosity. Furthermore, it has been found that by adding a thiol compound, it is possible to form a cured resin that does not easily turn yellow even under high temperature conditions such as soldering by a reflow method. The present invention has been completed based on these findings.
- the present invention is characterized in that the following component (A) and component (B) are contained at a blending ratio [the former / the latter (weight ratio)] of 70/30 to 99/1 and a thiol compound.
- a curable composition is provided.
- R 1 and R 3 are the same or different and each represents an alkylene group;
- R 2 and R 4 are the same or different;
- a hydrogen atom or a methyl group, n 1 and n 2 are the same or different and represent an integer of 0 or more)
- X represents a monovalent or divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, monocyclic aromatic hydrocarbon group, or a group to which these groups are bonded.
- R 5 represents an alkylene group.
- R 6 represents a hydrogen atom or a methyl group, n 3 represents an integer of 0 or more, n 4 represents 0 or 1, and n 5 represents 1 or 2.
- the compound represented by these is preferable.
- the viscosity at 25 ° C. is preferably 3600 mPa ⁇ s or less.
- the boiling point of the thiol compound is preferably 100 ° C. or higher, and the thiol compound is preferably a linear or branched alkanethiol or a linear or branched alkanedithiol.
- the curable composition is preferably thermosetting.
- the present invention also provides a cured resin obtained by curing the curable composition.
- the present invention further provides an optical member made of the cured resin.
- the curable composition of the present invention since it is excellent in fluidity before being cured, it is easy to uniformly apply to the mold while suppressing the generation of bubbles, and it is excellent in workability. Moreover, since it can harden rapidly by heating, the metal metal mold
- the cured resin thus obtained has an Abbe number of 30 or less, is excellent in transparency and heat resistance, and has an effect of suppressing yellowing even at a high temperature of about 260 ° C. Since the cured resin according to the present invention has the above characteristics, it is particularly suitable for the use of optical members such as lenses.
- the camera module can be simultaneously mounted in a soldering process (mounting process) by a reflow method. It becomes possible, and the connection process of the camera module by the connector performed after the soldering process can be omitted.
- the curable composition according to the present invention contains the following component (A) and component (B) as a curable monomer in a ratio of 70/30 to 99/1 in a compounding ratio [the former / the latter (weight ratio)] And a thiol compound.
- Component (A) in the present invention is a curable monomer represented by the above formula (1), having two (meth) acryloyloxy groups in the molecule, and having a fluorene ring.
- the rings Z 1 and Z 2 are the same or different and represent an aromatic carbocyclic ring.
- R 1 and R 3 are the same or different and represent an alkylene group, and
- R 2 and R 4 are the same or different and represent a hydrogen atom or a methyl group.
- n 1 and n 2 are the same or different and represent an integer of 0 or more.
- the fluorene ring, ring Z 1 and ring Z 2 may have a substituent.
- aromatic carbocycle in the ring Z 1 and the ring Z 2 examples include about 1 to 4 aromatic carbocycles such as a benzene ring, a naphthalene ring, and an anthracene ring.
- Preferred aromatic carbocycles include benzene rings, naphthalene rings and the like.
- alkylene group in R 1 and R 3 examples include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, trimethylene, tetramethylene and hexamethylene groups.
- Preferred alkylene groups include alkylene groups having 2 to 6 carbon atoms (particularly alkylene groups having 2 to 3 carbon atoms) such as ethylene, propylene and trimethylene groups.
- n 1 and n 2 is an integer of 0 or more, preferably an integer of 0 to 4, and preferably an integer of 1 to 4 in terms of lower viscosity and excellent fluidity.
- Examples of the substituent that the fluorene ring and ring Z 1 and ring Z 2 may have include alkyl groups such as methyl, ethyl, propyl and isopropyl groups (for example, C 1-6 alkyl groups, preferably methyl Group); cycloalkyl groups such as cyclopentyl and cyclohexyl groups (for example, C 5-8 cycloalkyl groups); aryl groups such as phenyl and naphthyl groups (for example, C 6-15 aryl groups); aralkyl groups such as benzyl groups ( For example, C 7-16 aralkyl group); acyl group such as acetyl, propionyl, benzoyl group (eg, C 1-10 acyl group); alkoxy group such as methoxy, ethoxy, propyloxy, isopropyloxy group (eg, C 1 -6 alkoxy group); methoxycarbonyl, alkoxycarbonyl groups such as
- Typical examples of the compound represented by formula (1) in the present invention having two (meth) acryloyloxy groups in the molecule and having a fluorene ring include the following compounds. it can. These can be used alone or in admixture of two or more.
- the ratio of the sum of the components (A) in the curable composition is 50 to 99% by weight, preferably 55 to 80% by weight, based on the entire curable monomer, although it varies depending on the use of the curable resin.
- the ratio of the sum total of the component (A) in a curable composition exceeds the said range, the fluidity
- the ratio of the sum total of the component (A) in a curable composition is less than the said range, there exists a tendency for heat resistance to fall.
- the component (B) in the present invention contains 50% by weight or more of the above-described component (A) having a high viscosity, thereby improving the fluidity of the curable composition.
- Examples of the monovalent aliphatic hydrocarbon group in X include 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups.
- alkyl group (Preferably 1 to 10, more preferably 1 to 3) alkyl group; vinyl, allyl, 1-butenyl group and the like having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3)
- An alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as an ethynyl group and a propynyl group.
- Examples of the monovalent alicyclic hydrocarbon group in X include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
- a cycloalkyl group of about 3 to 20 members such as cyclopentenyl and cyclohexenyl groups; a perhydronaphthalen-1-yl group, Norbornyl, adamantyl, bicyclo [3.3.0] octyl, tricyclo [5.2.1.0 2,6 ] decalyl, tricyclo [6.2.1.0 2,7 ] undecalyl, tetracyclo [4 4.0.1, 2,5 .
- a bridged cyclic hydrocarbon group such as a 1,7,10 ] dodecan-3-yl group.
- Examples of the monovalent monocyclic aromatic hydrocarbon group in X include aromatic hydrocarbon groups other than the condensed polycyclic aromatic hydrocarbon group such as a phenyl group and a 4-biphenyl group.
- Examples of the divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and monocyclic aromatic hydrocarbon group in X include the monovalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, and A corresponding group obtained by removing one hydrogen atom from a monocyclic aromatic hydrocarbon group can be exemplified.
- a monovalent or divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a monocyclic aromatic hydrocarbon group is bonded, two or more monovalent or divalent aliphatic hydrocarbon groups, Examples thereof include a group formed by bonding an alicyclic hydrocarbon group or a monocyclic aromatic hydrocarbon group via a single bond or a linking group.
- linking group examples include a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (—OCOO—), and these And a group in which a plurality of are bonded.
- the monovalent or divalent aliphatic hydrocarbon group, alicyclic hydrocarbon group, monocyclic aromatic hydrocarbon group, or the group hydrocarbon group to which these groups are bonded may be various substituents such as halogen atoms. , Oxo group, hydroxyl group, substituted oxy group (for example, alkoxy group, aryloxy group, aralkyloxy group, acyloxy group, etc.), carboxyl group, substituted oxycarbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group) Etc.), a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, an acyl group, a substituted or unsubstituted amino group, a sulfo group, a heterocyclic group and the like.
- hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis.
- a non-aromatic heterocycle may be condensed with a ring of an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
- R 5 in the formula (2) represents an alkylene group, and examples thereof include linear or branched alkylene groups having 1 to 10 carbon atoms such as methylene, ethylene, propylene, trimethylene, tetramethylene and hexamethylene groups.
- Preferred alkylene groups include linear or branched alkylene groups having 2 to 6 carbon atoms such as ethylene, propylene and trimethylene groups (particularly linear or branched alkylene groups having 2 to 3 carbon atoms). Is included.
- n 3 represents an integer of 0 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 4.
- n 5 represents 1 or 2.
- pulsation means an optically inhomogeneous state on the surface of the cured resin, and refers to a phenomenon in which wrinkles, fluctuations, irregularities and the like are observed on the surface of the cured resin.
- the viscosity of the component (B) in the present invention at 25 ° C. is preferably about 300 mPa ⁇ s or less, particularly 100 to 200 mPa ⁇ s, particularly preferably 100 to 150 mPa ⁇ s.
- the viscosity at 25 ° C. exceeds the above range, it tends to be difficult to improve the fluidity of the curable composition with a small amount of addition, and the fluidity is easy to work while maintaining optical properties in the curable composition. It tends to be difficult to impart the.
- the component (B) in the present invention is excellent in economic efficiency and maintains excellent optical properties (particularly, a low Abbe number, transparency, and refractive index) by being contained in the curable composition.
- the compound in which X in the formula (2) is a monovalent or divalent monocyclic aromatic hydrocarbon group is preferable in that the fluidity can be improved while suppressing the occurrence of pulse separation.
- X in the formula (2) represented by the above formulas (2b), (2c), (2d), (2p) is a monovalent monocyclic aromatic hydrocarbon group, and , Compounds wherein n 5 is 1 are preferred. These can be used alone or in admixture of two or more.
- the ratio of the sum of components (B) in the curable composition varies depending on the use of the curable resin, but is 1 to 30% by weight of the entire curable monomer, preferably 5 to 25% by weight, and most preferably Is from 5 to 20% by weight.
- the mixing ratio [former / latter (weight ratio)] of component (A) and component (B) in the curable composition is 70/30 to 99/1, preferably 75/25 to 95/5. Most preferably, it is 80/20 to 95/5.
- a thiol compound is mix
- the thiol compound includes a monothiol compound and a dithiol compound.
- radicals are generated in the polymer chain forming the cured resin by the generated peroxide. It is considered that this radical pulls out a hydrogen atom of the polymer chain to form a conjugated unsaturated bond, and yellowing occurs due to the formation of the conjugated unsaturated bond.
- the curable composition in the present invention contains a thiol together with a radical polymerizable compound having an aromatic ring, the thiol compound captures a peroxide generated at a high temperature, and a conjugated unsaturated bond formed on the polymer chain. It is presumed that the yellowing of the resin at high temperatures can be effectively suppressed because it has a function of eliminating the conjugated unsaturated bond through an enethiol reaction.
- the radical generated from the thiol compound is an electron-withdrawing radical, and the radical species involved in radical curing polymerization are also electron-withdrawing radicals.
- the chain transfer ability between electron-withdrawing radicals is not high, so unlike the case of using a phenolic antioxidant as a yellowing inhibitor, it is assumed that inhibition of radical curing polymerization is prevented. Is done.
- the curable composition according to the present invention is cured at a high curing rate, has excellent yellowing resistance, and suppresses the degree of yellowing to a very low level even when exposed to a high temperature of about 260 ° C., for example.
- a cured resin that can be formed can be formed.
- a thiol compound there is no volatilization or foaming when the curable composition is crosslinked and cured, and even if it is exposed to high temperature conditions in a cured resin (for example, in the reflow process) Heating)
- Those which are difficult to volatilize or foam are preferable, for example, those having a boiling point of 100 ° C. or higher, particularly those having a boiling point of 150 ° C. or higher, particularly those having a boiling point of 180 ° C. or higher.
- the term “boiling point” simply means the boiling point at normal pressure.
- thiol compound of the present invention it is preferable to use a neutral thiol compound as compared with an acidic or alkaline thiol compound in that the reactivity with the component (A) is mild and the storage stability is excellent. .
- a uniform curable composition can be obtained with high compatibility with the component (A) and the component (B) from the viewpoint that excellent optical properties can be imparted to the resulting cured resin.
- thiol compound examples include 1-hexanethiol (boiling point 150 ° C.), 1-heptanethiol (boiling point 177 ° C.), 1-octanethiol (boiling point 200 ° C.), tert-octanethiol (boiling point 156 ° C.), 1-nonane.
- dithiol compound examples include 1,4-butanedithiol (boiling point 195 ° C.), 2,3-butanedithiol (boiling point 87 ° C./50 mmHg), 1,5-pentanedithiol (108 ° C./15 mmHg) 1,6-hexane.
- Dithiol (boiling point 237 ° C), 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol (boiling point 297 ° C), 1,12-dodecanedithiol, 1,14 -Linear or branched alkanedithiol having about 4 to 30 carbon atoms (preferably about 4 to 20 carbon atoms) such as tetradecanedithiol, 1,16-hexadecanedithiol, 1,18-octadecanedithiol, etc. Can do.
- thiol compounds a linear alkanethiol or alkanedithiol having 10 to 15 carbon atoms such as decanethiol, dodecanethiol, and decanedithiol is preferable in that it can exhibit a more excellent yellowing suppression effect.
- decanethiol and decanedithiol are preferable.
- the amount of the thiol compound used can be appropriately adjusted within a range that does not impair the curability of the curable composition, and varies depending on the type of the thiol compound. It is about 10% by weight, preferably about 0.1 to 5% by weight, more preferably about 0.5 to 3% by weight.
- a thiol compound When there is too much usage-amount of a thiol compound, there exists a tendency for the sclerosis
- the amount of the thiol compound used is too small, the yellowing resistance of the cured resin tends to decrease.
- the curable composition of the present invention may contain a thermal radical polymerization initiator and other various additives depending on the use of the curable resin.
- thermal radical polymerization initiator examples include organic peroxides such as hydroperoxides, dialkyl peroxides, peroxyesters, diacyl peroxides, peroxydicarbonates, peroxyketals, and ketone peroxides. An oxide etc. can be mentioned. Specific examples of these thermal polymerization initiators include 1,1-di (t-butylperoxy) cyclohexane, dibenzoyl peroxide, t-butyl perbenzoate and the like. Of the thermal radical polymerization initiators, compounds such as azo radical polymerization initiators that generate gas components with the generation of radicals are not preferred because they leave bubbles in the cured resin.
- thermal radical polymerization initiator for example, trade name “Perhexa C” [1,1-di (t-butylperoxy) cyclohexane, manufactured by NOF Corporation], trade name “Perroyl L” [dilauroyl peroxide] Commercial products such as NOF Corporation] can be used.
- the blending amount of the thermal radical polymerization initiator is, for example, about 0.1 to 10% by weight, preferably about 0.1 to 5% by weight, based on the entire curable composition.
- additives include, for example, curable monomers other than the above components (A) and (B), organosiloxane compounds, metal oxide particles, rubber particles, silicone-based and fluorine-based antifoaming agents, and silane coupling agents. , Fillers, plasticizers, leveling agents, antistatic agents, mold release agents, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbers, pigments and the like.
- the compounding quantity of these various additives is 5 weight% or less with respect to the whole curable composition, for example.
- the curable composition of the present invention may contain a solvent, but if it is too much, bubbles may be formed in the cured resin. Therefore, it is preferably 10% by weight or less, particularly 1% by weight based on the entire curable composition. It is as follows.
- the curable composition of the present invention includes, for example, a predetermined amount of component (A), component (B), and thiol compound, and if necessary, a thermal radical polymerization initiator, various additives, and the like. Accordingly, it is prepared by stirring and mixing while excluding bubbles under vacuum.
- the temperature at the time of stirring and mixing is, for example, about 10 to 60 ° C.
- a known apparatus such as a rotation / revolution mixer, a single-screw or multi-screw extruder, a planetary mixer, a kneader, or a dissolver can be used.
- the viscosity at 25 ° C. of the curable composition according to the present invention is 3600 mPa ⁇ s or less, preferably 2000 mPa ⁇ s or less, more preferably 1500 mPa ⁇ s or less, and particularly preferably 1000 mPa ⁇ s or less.
- the viscosity exceeds the above range, the fluidity is lowered and bubbles are likely to remain, and the casting property to the mold is lowered due to a decrease in coating property and filling property, and an increase in injection pressure. For this reason, it takes time to adjust the handling temperature, defoaming, and curing conditions (curing temperature, curing time, heating rate, cooling rate, etc.). Sex is reduced.
- the curable composition prepared by the above method can be molded by a conventionally known molding method such as a casting method or an injection molding method, and then promotes a radical polymerization reaction by heating to obtain a cured resin. .
- the heating temperature is about 80 to 200 ° C. (preferably about 110 to 160 ° C.), and the heating time is about 1 to 5 minutes (preferably about 1 to 3 minutes).
- the curable composition according to the present invention has fast curability and can form a cured resin very quickly by heating under the above heating conditions.
- the curing rate of the cured resin according to the present invention measured by the DSC method is, for example, preferably 70% or more (preferably 80% or more) at 150 ° C. for 5 minutes. It is preferably 70% or more (preferably 80% or more) per minute.
- the curable composition according to the present invention is excellent in fluidity, it can be suitably used particularly for a casting method. Therefore, the curable composition can be used efficiently as compared with the case of the injection molding method, and it is economical, and a cured resin having a desired shape can be produced speedily.
- the curable composition according to the present invention is thermosetting, a metal mold can be used for molding.
- a metal mold can be easily finer and finer than a glass mold or the like. Therefore, according to the curable composition of the present invention, a cured resin having a minute and dense shape can be easily formed.
- the cured resin of the present invention obtained by the above method is excellent in transparency.
- the internal transmittance (%) at 400 nm is 90% or more, preferably 95% or more, particularly preferably. 98% or more.
- the cured resin of the present invention is excellent in yellowing resistance.
- the yellowing rate after a heat resistance test is 2% or less, preferably 1.5% or less, particularly preferably 0.5% or less for a cured resin having a thickness of 0.5 mm. Is 1.0% or less.
- the yellowing rate in this invention is represented by the decreasing degree of the internal transmittance in 400 nm before and behind the following heat resistance test, and is calculated
- the cured resin of the present invention is excellent in heat resistance, for example, the glass transition temperature is 100 ° C. or higher, preferably 110 to 170 ° C.
- the Abbe number of the cured resin of the present invention is 30 or less, preferably 28 or less, particularly preferably 27 or less.
- the refractive index of the lens varies depending on the wavelength of light, and a phenomenon (chromatic aberration) that causes a shift (bleed or blur) in the image occurs.
- a normal lens has a structure that corrects chromatic aberration by combining a lens resin having a high Abbe number and a lens resin having a low Abbe number.
- the glass of a lens used in a camera is classified into two types according to the Abbe number. Generally, those having an Abbe number of 50 or less are called flint glass, and those having 50 or more are called crown glass.
- the cured resin of the present invention can be suitably used as a low Abbe number lens resin.
- the cured resin of the present invention is excellent in transparency and heat resistance, and is suitably used as an optical member because yellowing is remarkably suppressed even at a high temperature of about 260 ° C., for example.
- the optical member include an imaging lens, a spectacle lens, a filter, a diffraction grating, a prism, a light guide, and a light beam collection for a camera (on-vehicle camera, digital camera, PC camera, mobile phone camera, surveillance camera, etc.).
- Optical lens, light diffusion lens, cover glass for display device photo sensor, photo switch, LED, light emitting element, optical waveguide, optical splitter, optical fiber adhesive, display element substrate, color filter substrate, touch panel substrate, Examples thereof include a display protective film, a display backlight, a light guide plate, and an antireflection film.
- EA-F5503 Diluted solution of benzyl acrylate of the compound represented by the following formula (1a) (content of the compound represented by the following formula (1a): 73% by weight), trade name “Ogsol EA-F5503”, Osaka Gas EA-0200 manufactured by Chemical Co., Ltd .: 95% by weight of a compound represented by the following formula (1b), trade name “Ogsol EA-0200”, manufactured by Osaka Gas Chemical Co., Ltd.
- the curable compositions obtained in the examples and comparative examples were poured into a 0.5 mm-thick mold previously coated with a release agent and vapor-deposited, and preheated to 200 ° C. in an air atmosphere And then heated in an oven preheated to 140 ° C. for 2 minutes to release the mold. Thereafter, post-baking was further performed at 160 ° C. for 30 minutes to obtain cured resins (5 pieces each).
- the light transmittance at 400 nm was measured using a spectrophotometer (trade name “U-3900” manufactured by Hitachi High-Technologies Corporation).
- n is the refractive index at 400 nm, and the value of the refractive index at 400 nm measured by the following method was used.
- the refractive index of the curable resin was measured by measuring the refractive index at 589 nm at 25 ° C. using a refractometer (trade name “Model 2010”, manufactured by Metricon) in accordance with JIS K7142.
- Abbe number (n d ⁇ 1) / (n f ⁇ n c )
- n d represents a refractive index at 589.2 nm
- n f represents a refractive index at 486.1 nm
- n c represents a refractive index at 656.3 nm.
- the value of the refractive index in each wavelength measured by the said method was used for the refractive index.
- Glass-transition temperature The glass transition temperature of the cured resin is increased by a pre-treatment (from ⁇ 50 ° C. to 250 ° C. at a rate of 20 ° C./min.) Using a differential scanning calorimeter (trade name “Q2000”, manufactured by TA Instruments). Subsequently, the temperature was lowered from 250 ° C. to ⁇ 50 ° C. at ⁇ 20 ° C./min), and the temperature was measured at a temperature rising rate of 20 ° C./min and a measurement temperature range of ⁇ 50 ° C. to 250 ° C.
- Linear expansion coefficient The linear expansion coefficient of the cured resin was measured using a TMA measuring device (trade name “TMA / SS100”, manufactured by SII NanoTechnology Co., Ltd.), with a temperature increase rate of 5 ° C./min and a measurement temperature range of 30 ° C. to 250 ° C. The rate was measured and the slope of the straight line on the low temperature side was expressed as the coefficient of linear expansion. Moreover, the description in Table 2 is shown by linear expansion coefficient (ppm / ° C.) below the glass transition temperature / linear expansion coefficient (ppm / ° C.) above the glass transition temperature.
- the curable composition of the present invention since it is excellent in fluidity before being cured, it can be uniformly applied to the mold while suppressing the generation of bubbles. Moreover, since it can harden rapidly by heating, the metal metal mold
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Abstract
Description
成分(A):下記式(1)
で表される、分子内に2個の(メタ)アクリロイルオキシ基を有し、且つ、フルオレン環を有する化合物
成分(B):分子内にビニル基若しくは(メタ)アクリロイルオキシ基を少なくとも1つ有し、且つ、フルオレン環を有しない化合物 That is, the present invention is characterized in that the following component (A) and component (B) are contained at a blending ratio [the former / the latter (weight ratio)] of 70/30 to 99/1 and a thiol compound. A curable composition is provided.
Component (A): Formula (1) below
A compound having two (meth) acryloyloxy groups in the molecule and having a fluorene ring Component (B): having at least one vinyl group or (meth) acryloyloxy group in the molecule And a compound having no fluorene ring
で表される化合物が好ましい。 As the component (B), the following formula (2)
The compound represented by these is preferable.
本発明における成分(A)は、上記式(1)で表され、分子内に2個の(メタ)アクリロイルオキシ基を有し、且つ、フルオレン環を有する硬化性モノマーである。式(1)中、環Z1、Z2は同一又は異なって、芳香族炭素環を示す。R1、R3は同一又は異なって、アルキレン基を示し、R2、R4は同一又は異なって、水素原子又はメチル基を示す。n1、n2は同一又は異なって、0以上の整数を示す。フルオレン環、及び環Z1、環Z2は置換基を有していてもよい。 [Component (A)]
Component (A) in the present invention is a curable monomer represented by the above formula (1), having two (meth) acryloyloxy groups in the molecule, and having a fluorene ring. In formula (1), the rings Z 1 and Z 2 are the same or different and represent an aromatic carbocyclic ring. R 1 and R 3 are the same or different and represent an alkylene group, and R 2 and R 4 are the same or different and represent a hydrogen atom or a methyl group. n 1 and n 2 are the same or different and represent an integer of 0 or more. The fluorene ring, ring Z 1 and ring Z 2 may have a substituent.
本発明における成分(B)は、粘度の高い上記成分(A)を50重量%以上含む本発明に係る硬化性組成物において、配合することにより、硬化性組成物の流動性を向上させる働きを有する硬化性モノマーであり、分子内にビニル基若しくは(メタ)アクリロイルオキシ基を少なくとも1つ有し、且つ、フルオレン環を有しないことを特徴とする。 [Component (B)]
In the curable composition according to the present invention, the component (B) in the present invention contains 50% by weight or more of the above-described component (A) having a high viscosity, thereby improving the fluidity of the curable composition. A curable monomer having at least one vinyl group or (meth) acryloyloxy group in the molecule and having no fluorene ring.
本発明では、硬化性組成物中にチオール化合物を配合することを特徴とする。チオール化合物にはモノチオール化合物、ジチオール化合物が含まれる。 [Thiol compound]
In this invention, a thiol compound is mix | blended in a curable composition, It is characterized by the above-mentioned. The thiol compound includes a monothiol compound and a dithiol compound.
本発明の硬化性組成物は、硬化樹脂の用途に応じて、熱ラジカル重合開始剤やその他各種添加剤を添加してもよい。 [Other ingredients]
The curable composition of the present invention may contain a thermal radical polymerization initiator and other various additives depending on the use of the curable resin.
耐熱性試験:厚さ0.5mmの硬化樹脂を、シンアペック社製卓上リフロー炉を使用して、JEDEC規格記載のリフロー温度プロファイルに基づく耐熱性試験を連続して3回繰り返す
黄変率(%)={(耐熱性試験前の内部透過率)-(耐熱性試験後の内部透過率)}/(耐熱性試験前の内部透過率)×100 The cured resin of the present invention is excellent in yellowing resistance. For example, the yellowing rate after a heat resistance test is 2% or less, preferably 1.5% or less, particularly preferably 0.5% or less for a cured resin having a thickness of 0.5 mm. Is 1.0% or less. In addition, the yellowing rate in this invention is represented by the decreasing degree of the internal transmittance in 400 nm before and behind the following heat resistance test, and is calculated | required by the following formula.
Heat resistance test: Repeated heat resistance test based on the reflow temperature profile described in the JEDEC standard three times using a table reflow oven manufactured by Shinapec Co., Ltd. with a thickness of 0.5 mm. Yellowing rate (%) = {(Internal transmittance before heat resistance test)-(Internal transmittance after heat resistance test)} / (Internal transmittance before heat resistance test) × 100
下記表1に記載の各成分を配合組成(数値は重量部)に従って配合し、自転公転型ミキサーで撹拌・混合することにより均一で透明な硬化性組成物を得た。
Each component shown in the following Table 1 was blended according to the blending composition (numerical values are parts by weight), and stirred and mixed with a rotation / revolution mixer to obtain a uniform and transparent curable composition.
[成分(A)]
EA-F5503:下記式(1a)で表される化合物のベンジルアクリレート希釈液(下記式(1a)で表される化合物の含有量:73重量%)、商品名「オグソール EA-F5503」、大阪ガスケミカル(株)製
EA-0200:下記式(1b)で表される化合物を95重量%含有、商品名「オグソール EA-0200」、大阪ガスケミカル(株)製
[成分(B)]
DVE:下記式(2a)で表されるジビニルベンゼン
IRR214K:下記式(2j)で表される化合物、商品名「IRR214K」、ダイセル・サイテック(株)製
A-LEN-10:下記式(2c)で表される化合物、商品名「A-LEN-10」、新中村化学(株)製
[熱ラジカル重合開始剤]
パーヘキサC80:商品名「パーヘキサC-80」、1,1-ジ(t-ブチルパーオキシ)シクロヘキサン、日油(株)製
[その他]
Irg1010:商品名「Irganox1010」、チバ・スペシャリティーケミカルズ社製
[Component (A)]
EA-F5503: Diluted solution of benzyl acrylate of the compound represented by the following formula (1a) (content of the compound represented by the following formula (1a): 73% by weight), trade name “Ogsol EA-F5503”, Osaka Gas EA-0200 manufactured by Chemical Co., Ltd .: 95% by weight of a compound represented by the following formula (1b), trade name “Ogsol EA-0200”, manufactured by Osaka Gas Chemical Co., Ltd. [Component (B)]
DVE: divinylbenzene represented by the following formula (2a) IRR214K: compound represented by the following formula (2j), trade name “IRR214K”, manufactured by Daicel Cytec Co., Ltd. A-LEN-10: the following formula (2c) A compound represented by the trade name “A-LEN-10”, manufactured by Shin-Nakamura Chemical Co., Ltd. [thermal radical polymerization initiator]
Perhexa C80: Trade name “Perhexa C-80”, 1,1-di (t-butylperoxy) cyclohexane, manufactured by NOF Corporation [Others]
Irg1010: Trade name “Irganox1010”, manufactured by Ciba Specialty Chemicals
硬化性組成物の粘度は、レオメーター(商品名「PHYSICA UDS200」、Paar Physica社製)を使用し、25℃、回転速度D=20/s時点の粘度(mPa・s)を測定した。 [viscosity]
The viscosity of the curable composition was measured using a rheometer (trade name “PHYSICA UDS200”, manufactured by Paar Physica) at 25 ° C. and a rotation speed D = 20 / s (mPa · s).
実施例及び比較例で得られた硬化性組成物を10mLシリンジに注入し、減圧下で自転公転型ミキサーを使用して脱泡した。その後、高精度液剤塗布装置(商品名「ディスペンサーultra2400」、EFD社製)を使用して、幅1.0mmに調整した隙間への塗布をそれぞれ5回ずつ行い、下記基準に従って評価した。
評価基準
5回全てについて気泡が観察されなかった:◎
5回のうち、1~2回気泡が観察された:○
5回のうち、3~4回気泡が観察された:△
5回全てに気泡が観察された:× [Applicability]
The curable compositions obtained in Examples and Comparative Examples were injected into a 10 mL syringe and defoamed using a rotation and revolution type mixer under reduced pressure. Thereafter, using a high-precision liquid application device (trade name “dispenser ultra2400”, manufactured by EFD), application to the gap adjusted to a width of 1.0 mm was performed 5 times each and evaluated according to the following criteria.
Evaluation criteria Bubbles were not observed for all 5 times: ◎
Bubbles were observed 1 to 2 times out of 5 times: ○
Out of 5 bubbles were observed 3-4 times: △
Bubbles were observed in all 5 times: ×
上記により得られた硬化樹脂の表面を目視で観察し、下記基準に従って評価した。
評価基準
5個全てについて脈離が観察されなかった:◎
5個のうち、1~2個に脈離が観察された:○
5個のうち、3~4個に脈離が観察された:△
5個全てに脈離が観察された:× [Resin surface shape]
The surface of the cured resin obtained as described above was visually observed and evaluated according to the following criteria.
Evaluation criteria No pulse was observed for all five:
Disruption was observed in 1-2 of 5:
Out of five, 3-4 were observed to be isolated: △
Disruption was observed in all five: ×
硬化樹脂について、内部透過率を下記式によって算出した。
内部透過率(400nm)=400nmにおける光線透過率/(1-r)2
r={(n-1)/(n+1)}2
400nmにおける光線透過率は分光光度計(日立ハイテクノロジーズ社製、商品名「U-3900」)を用いて測定した。nは400nmにおける屈折率であり、下記方法で測定した400nmにおける屈折率の値を用いた。 [Internal transmittance]
For the cured resin, the internal transmittance was calculated by the following formula.
Internal transmittance (400 nm) = light transmittance at 400 nm / (1-r) 2
r = {(n−1) / (n + 1)} 2
The light transmittance at 400 nm was measured using a spectrophotometer (trade name “U-3900” manufactured by Hitachi High-Technologies Corporation). n is the refractive index at 400 nm, and the value of the refractive index at 400 nm measured by the following method was used.
硬化樹脂の屈折率は、JIS K7142に準拠した方法で、屈折率計(商品名「Model 2010」、メトリコン社製)を用いて、25℃における589nmの屈折率を測定した。 [Refractive index]
The refractive index of the curable resin was measured by measuring the refractive index at 589 nm at 25 ° C. using a refractometer (trade name “Model 2010”, manufactured by Metricon) in accordance with JIS K7142.
硬化樹脂のアッベ数は下の式によって算出した。
アッベ数=(nd-1)/(nf-nc)
式中、ndは589.2nmにおける屈折率、nfは486.1nmにおける屈折率、ncは656.3nmにおける屈折率を示す。なお、屈折率は、上記方法で測定した各波長における屈折率の値を用いた。 [Abbe number]
The Abbe number of the cured resin was calculated by the following formula.
Abbe number = (n d −1) / (n f −n c )
In the formula, n d represents a refractive index at 589.2 nm, n f represents a refractive index at 486.1 nm, and n c represents a refractive index at 656.3 nm. In addition, the value of the refractive index in each wavelength measured by the said method was used for the refractive index.
硬化樹脂のガラス転移温度は、示差走査熱量測定装置(商品名「Q2000」、ティー・エイ・インスツルメント社製)を用い、事前処理(-50℃から250℃まで20℃/分で昇温し、続いて250℃から-50℃まで-20℃/分で降温)を行った後に、昇温速度20℃/分、測定温度範囲-50℃~250℃で測定した。 [Glass-transition temperature]
The glass transition temperature of the cured resin is increased by a pre-treatment (from −50 ° C. to 250 ° C. at a rate of 20 ° C./min.) Using a differential scanning calorimeter (trade name “Q2000”, manufactured by TA Instruments). Subsequently, the temperature was lowered from 250 ° C. to −50 ° C. at −20 ° C./min), and the temperature was measured at a temperature rising rate of 20 ° C./min and a measurement temperature range of −50 ° C. to 250 ° C.
硬化樹脂の線膨張係数は、TMA測定装置(商品名「TMA/SS100」、エスアイアイ・ナノテクノロジー社製)を用い、昇温速度5℃/min、測定温度範囲30℃~250℃で熱膨張率を測定し、低温側の直線の勾配を線膨張係数として表した。また、表2中の記載は、ガラス転移温度以下での線膨張係数(ppm/℃)/ガラス転移温度以上での線膨張係数(ppm/℃)で示した。 [Linear expansion coefficient]
The linear expansion coefficient of the cured resin was measured using a TMA measuring device (trade name “TMA / SS100”, manufactured by SII NanoTechnology Co., Ltd.), with a temperature increase rate of 5 ° C./min and a measurement temperature range of 30 ° C. to 250 ° C. The rate was measured and the slope of the straight line on the low temperature side was expressed as the coefficient of linear expansion. Moreover, the description in Table 2 is shown by linear expansion coefficient (ppm / ° C.) below the glass transition temperature / linear expansion coefficient (ppm / ° C.) above the glass transition temperature.
硬化樹脂を、シンアペック社製卓上リフロー炉を使用して、JEDEC規格記載のリフロー温度プロファイルに基づく耐熱性試験を連続して3回行った後、上記方法により400nmにおける光線透過率及び屈折率を測定し、耐熱性試験後における内部透過率を求め、耐熱性試験前後の内部透過率から、黄変率(%)を下記式により求め、耐熱性を評価した。
黄変率(%)={(耐熱性試験前の内部透過率)-(耐熱性試験後の内部透過率)}/(耐熱性試験前の内部透過率)×100 [Heat resistance test]
The cured resin was subjected to a heat resistance test based on the JEDEC standard reflow temperature profile three times in succession using a tabletop reflow oven manufactured by Shin-Apec Co., Ltd., and the light transmittance and refractive index at 400 nm were measured by the above method. Then, the internal transmittance after the heat resistance test was obtained, and the yellowing rate (%) was obtained from the internal transmittance before and after the heat resistance test by the following formula, and the heat resistance was evaluated.
Yellowing rate (%) = {(Internal transmittance before heat resistance test) − (Internal transmittance after heat resistance test)} / (Internal transmittance before heat resistance test) × 100
Claims (8)
- 下記成分(A)及び成分(B)を配合比[前者/後者(重量比)]が70/30~99/1の割合で含有し、且つチオール化合物を含有することを特徴とする硬化性組成物。
成分(A):下記式(1)
で表される、分子内に2個の(メタ)アクリロイルオキシ基を有し、且つ、フルオレン環を有する化合物
成分(B):分子内にビニル基若しくは(メタ)アクリロイルオキシ基を少なくとも1つ有し、且つ、フルオレン環を有しない化合物 A curable composition comprising the following component (A) and component (B) in a mixing ratio [the former / the latter (weight ratio)] of 70/30 to 99/1 and a thiol compound: object.
Component (A): Formula (1) below
A compound having two (meth) acryloyloxy groups in the molecule and having a fluorene ring Component (B): having at least one vinyl group or (meth) acryloyloxy group in the molecule And a compound having no fluorene ring - 成分(B)が、下記式(2)
で表される化合物である請求項1に記載の硬化性組成物。 Component (B) is represented by the following formula (2)
The curable composition of Claim 1 which is a compound represented by these. - 25℃における粘度が3600mPa・s以下である請求項1又は2に記載の硬化性組成物。 The curable composition according to claim 1 or 2, wherein the viscosity at 25 ° C is 3600 mPa · s or less.
- チオール化合物の沸点が100℃以上である請求項1~3の何れかの項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 3, wherein the boiling point of the thiol compound is 100 ° C or higher.
- チオール化合物が直鎖状若しくは分岐鎖状のアルカンチオール又は、直鎖状若しくは分岐鎖状のアルカンジチオールである請求項1~4の何れかの項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 4, wherein the thiol compound is a linear or branched alkanethiol or a linear or branched alkanedithiol.
- 熱硬化性である請求項1~5の何れかの項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 5, which is thermosetting.
- 請求項1~6の何れかの項に記載の硬化性組成物を硬化して得られる硬化樹脂。 A cured resin obtained by curing the curable composition according to any one of claims 1 to 6.
- 請求項7に記載の硬化樹脂からなる光学部材。 An optical member made of the cured resin according to claim 7.
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WO2011102286A1 (en) * | 2010-02-16 | 2011-08-25 | ダイセル化学工業株式会社 | Curable composition and cured material |
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- 2011-08-01 JP JP2012528642A patent/JP5840611B2/en active Active
- 2011-08-01 CN CN2011800386868A patent/CN103097456A/en active Pending
- 2011-08-01 WO PCT/JP2011/067596 patent/WO2012020659A1/en active Application Filing
- 2011-08-08 TW TW100128130A patent/TW201211078A/en unknown
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Cited By (4)
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US20180050973A1 (en) * | 2013-03-29 | 2018-02-22 | Tokyo Ohka Kogyo Co., Ltd. | Vinyl-group-containing fluorene compound |
WO2016047766A1 (en) * | 2014-09-26 | 2016-03-31 | 東京応化工業株式会社 | Transparent body production method, transparent body, and amorphous body |
JPWO2016047766A1 (en) * | 2014-09-26 | 2017-07-06 | 東京応化工業株式会社 | Method for producing transparent body, transparent body and amorphous body |
US10322989B2 (en) | 2014-09-26 | 2019-06-18 | Tokyo Ohka Kogyo Co., Ltd. | Transparent body production method, transparent body, and amorphous body |
Also Published As
Publication number | Publication date |
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JP5840611B2 (en) | 2016-01-06 |
KR20130097180A (en) | 2013-09-02 |
CN103097456A (en) | 2013-05-08 |
TW201211078A (en) | 2012-03-16 |
JPWO2012020659A1 (en) | 2013-10-28 |
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