WO2017068988A1 - 活性エネルギー線硬化型組成物及びプラスチックレンズ - Google Patents
活性エネルギー線硬化型組成物及びプラスチックレンズ Download PDFInfo
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- WO2017068988A1 WO2017068988A1 PCT/JP2016/079762 JP2016079762W WO2017068988A1 WO 2017068988 A1 WO2017068988 A1 WO 2017068988A1 JP 2016079762 W JP2016079762 W JP 2016079762W WO 2017068988 A1 WO2017068988 A1 WO 2017068988A1
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- Prior art keywords
- acrylate
- meth
- active energy
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- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000524 functional group Chemical group 0.000 claims abstract description 37
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- 230000008016 vaporization Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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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
- 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
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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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
- 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
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
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- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- 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
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
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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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
Definitions
- the present invention relates to an active energy ray-curable composition having a low viscosity suitable for coating and having a high refractive index in the cured product, the cured product, and a plastic lens.
- N-vinylcarbazole As a prism sheet material having a high refractive index, a composition containing N-vinylcarbazole or a derivative thereof is known (Patent Document 3 below).
- N-vinylcarbazole itself is highly crystalline and difficult to handle, and the refractive index of a cured product obtained by curing this composition is not at a sufficient level.
- the conventional high refractive index type polymerizable compound has a viscosity of the compound itself that is easily increased or crystallized. It could not be raised enough.
- the problem to be solved by the present invention is to provide an active energy ray-curable composition having a low viscosity suitable for coating and having a high refractive index in the cured product, the cured product, and a plastic lens. It is in.
- an active energy ray-curable composition containing phenylbenzyl (meth) acrylate and a bicarbazole compound is applied even if it is a solvent-free system.
- the present invention has been completed by finding that the cured product has a low viscosity suitable for construction and has a high refractive index.
- the present invention includes phenylbenzyl (meth) acrylate (A) and the following structural formula (1).
- X 1 and X 2 are each independently a photopolymerizable functional group, a structural portion having a photopolymerizable functional group, or a hydrogen atom, and at least one of them is a photopolymerizable functional group or photopolymerization.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom. is there.
- the present invention further relates to a cured product of the active energy ray-curable composition.
- the present invention further relates to a plastic lens made of a cured product of the active energy ray-curable composition.
- an active energy ray-curable composition having a low viscosity suitable for coating and having a high refractive index in the cured product, the cured product, and a plastic lens can be provided.
- FIG. 1 is a 1H-NMR chart of the bicarbazole compound (B-1) obtained in Production Example 2.
- the active energy ray-curable resin composition of the present invention comprises phenylbenzyl (meth) acrylate (A) and the following structural formula (1)
- X 1 and X 2 are each independently a photopolymerizable functional group, a structural portion having a photopolymerizable functional group, or a hydrogen atom, and at least one of them is a photopolymerizable functional group or photopolymerization.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom. is there.
- Examples of the phenylbenzyl (meth) acrylate (A) include orthophenylbenzyl (meth) acrylate, metaphenylbenzyl (meth) acrylate, and paraphenylbenzyl (meth) acrylate.
- these compounds may be used alone or in combination of two or more.
- orthophenylbenzyl (meth) acrylate and metaphenylbenzyl (meth) acrylate have a liquid refractive index of 1.57 or more at 25 ° C. and a viscosity of 30 mPa ⁇ s or less, which is relatively high.
- Paraphenylbenzyl acrylate is solid at room temperature, but is preferable in that the refractive index of the liquid at 40 ° C. is as high as 1.59 or more.
- the low viscosity of the composition and the high refractive index of the cured product can be combined at a high level, orthophenylbenzyl (meth) acrylate, metaphenylbenzyl (meth) acrylate and paraphenylbenzyl (meth) It is preferable to use acrylate together.
- the radical polymerizable composition having a sufficiently high refractive index in the cured product can be obtained with a low viscosity, the orthophenylbenzyl (meth) acrylate and the metaphenylbenzyl (meth) acrylate,
- the molar ratio [ ⁇ [orthophenylbenzyl (meth) acrylate] + [metaphenylbenzyl (meth) acrylate] ⁇ / [paraphenylbenzyl (meth) acrylate]] with paraphenylbenzyl (meth) acrylate is 55/45 to 10 It is preferable to use it in the range of / 90.
- orthophenylbenzyl (meth) acrylate and paraphenylbenzyl (meth) acrylate are easier to produce, it is particularly preferable to use them in combination.
- the blending ratio is low viscosity, but a radical polymerizable composition having a sufficiently high refractive index in the cured product can be obtained. Therefore, orthophenylbenzyl (meth) acrylate, paraphenylbenzyl (meth) acrylate and The molar ratio [[orthophenylbenzyl (meth) acrylate]] / [paraphenylbenzyl (meth) acrylate]] is preferably in the range of 55/45 to 10/90.
- the phenylbenzyl (meth) acrylate (A) can be produced by, for example, a method of esterifying biphenylmethanol and (meth) acrylic acid (method 1), or a halogenation such as chloromethylbiphenyl or bromomethylbiphenyl.
- a method of reacting methylbiphenyl with an alkali metal salt such as potassium, sodium, or lithium (meth) acrylic acid Method 2
- Method 3 a method of reacting with acrylic acid or an alkali metal acrylate
- the reaction ratio of biphenyl and formaldehyde is 1 to 25 mol of formaldehyde with respect to 1 mol of biphenyl.
- Formaldehyde may be used in any form such as formalin aqueous solution, paraformaldehyde, trioxane.
- the hydrogen halide include concentrated hydrochloric acid and hydrogen chloride gas, and it is preferably used in an excess molar ratio with respect to biphenyl.
- the reaction is preferably performed under acid catalyst conditions.
- the acid catalyst used examples include sulfuric acid, phosphoric acid, polyphosphoric acid, trichloroacetic acid, dichloroacetic acid, monochloroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, and zinc chloride. And Lewis acid. If necessary, the reaction may be carried out in an organic solvent such as dimethoxyethane, dioxane, cyclopentylmethyl ether, and acetic acid, and the reaction temperature is preferably in the range of 60 to 180 ° C.
- phenylbenzyl (meth) acrylate (A) is produced by such a method, in addition to the phenylbenzyl (meth) acrylate (A), bis [(meth) acryloylmethyl] biphenyl (A ′) or biphenyl structure is methylene. In some cases, a biphenyl compound (A ′′) having a molecular structure knotted via a by-product may be by-produced.
- the content of phenylbenzyl (meth) acrylate (A) in 100 parts by mass of the reaction product is 30 It is preferably in the range of -95 parts by mass, more preferably in the range of 35-85 parts by mass, and the bis [(meth) acryloylmethyl] biphenyl (A ′) in 100 parts by mass of the reaction product.
- the content is preferably in the range of 5 to 70 parts by mass, more preferably in the range of 15 to 65 parts by mass.
- the content of the biphenyl compound (A ′′) having a molecular structure in which the biphenyl structure is knotted through methylene in 100 parts by mass of the composition is preferably in the range of 0.5 to 30 parts by mass. More preferably, it is in the range of parts by mass.
- the phenylbenzyl (meth) acrylate (A) when the phenylbenzyl (meth) acrylate (A) is produced by such a method, unreacted raw material biphenyl may remain in the reaction product.
- the biphenyl content in 100 parts by mass of the reaction product is in the range of 0.5 to 15 parts by mass. Is preferable, and the range of 1 to 10 parts by mass is more preferable.
- Examples of the method for measuring the content of each component in the reaction product include a gas chromatograph, a liquid chromatograph, a gel permeation chromatograph, and the like.
- the bis [(meth) acryloylmethyl] biphenyl (A ′) is, for example, 2,2′-bis (acryloylmethyl) -1,1′-biphenyl, 3,3′-bis (acryloylmethyl) -1,1 '-Biphenyl, 4,4'-bis (acryloylmethyl) -1,1'-biphenyl, 2,4'-bis (acryloylmethyl) -1,1'-biphenyl, 2,4-bis (acryloylmethyl)- Examples include 1,1′-biphenyl, 2,6-bis (acryloylmethyl) -1,1′-biphenyl, and the like.
- the number of biphenyl structural units contained in the molecular structure is preferably in the range of 2 to 5.
- the biphenyl compound (A) is, for example, a component obtained by removing the phenylbenzyl (meth) acrylate (A) and the bis (acryloylmethyl) biphenyl (A ′) from the reaction product by silica gel column chromatography, Examples of the method include analysis using a gas chromatograph mass spectrometer (GC-MS) and a high performance liquid chromatograph mass spectrometer (LC-MS).
- GC-MS gas chromatograph mass spectrometer
- LC-MS high performance liquid chromatograph mass spectrometer
- the bicarbazole compound (B) has the following structural formula (1)
- X 1 and X 2 are each independently a photopolymerizable functional group, a structural portion having a photopolymerizable functional group, or a hydrogen atom, and at least one of them is a photopolymerizable functional group or photopolymerization.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom. is there.
- the carbazole structure has a structure in which the 1-position carbon atom and the 3-position carbon atom are bonded. Such a compound is difficult to crystallize, has high compatibility with other compounds such as the phenylbenzyl (meth) acrylate (A), and has a remarkably high refractive index in the cured product.
- Each of R 1 and R 2 in the structural formula (1) is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or chlorine atom. Especially, since it becomes excellent in compatibility with another compound and becomes a compound with a high refractive index in a cured product, it is preferable that either R 1 or R 2 is a hydrogen atom.
- the other of R 1 and R 2 is preferably any one of a methyl group, an ethyl group, a propyl group, a t-butyl group, a methoxy group, a chlorine atom, or a bromine atom.
- X 1 and X 2 in the structural formula (1) are each independently a photopolymerizable functional group, a structural site having a photopolymerizable functional group, or a hydrogen atom.
- the photopolymerizable functional group include radical polymerizable functional groups such as vinyl group and acryloyl group; and photocation polymerizable functional groups such as glycidyl group and 2-methylglycidyl group.
- the structural moiety having the photopolymerizable functional group includes, for example, a structural moiety having a photocationically polymerizable group such as 3-methyloxetanyl-methyl group, 3-ethyloxetanyl-methyl group, and the following structural formula (2)
- R 3 represents an alkylene group having 2 to 6 carbon atoms
- R 4 represents a hydrogen atom or a methyl group
- n is an integer of 0 to 10
- a structural site having a radically polymerizable functional group such as a (meth) acryloyl group-containing structural site.
- the (meth) acryloyl group-containing structural site examples include a (meth) acryloyloxyethyl group, a (meth) acryloylpolyoxyethylene group, a (meth) acryloyloxypropylene group, a (meth) acryloylpolyoxypropylene group, and the like. Is mentioned. Among these, a (meth) acryloyloxyethyl group is preferable because of excellent reactivity and a high refractive index in the cured product.
- radical polymerizable functional group when the above-mentioned radical polymerizable functional group is compared with the photocation polymerizable functional group, the radical polymerizable functional group is preferable from the viewpoint of excellent curability.
- one of X 1 and X 2 in the structural formula (1) may be a hydrogen atom, but in the present invention, both X 1 and X 2 are photopolymerizable functional groups or photopolymerization. It is preferable from the point which is excellent in sclerosis
- bicarbazole compound examples include, for example, those in which X 1 and X 2 in the structural formula (1) are vinyl groups represented by the following structural formulas (I-1) to (I-5)
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- the compounds represented by (IV to 5) are preferred from the viewpoint of excellent curability.
- the bicarbazole compound (B) is preferably a compound having no substituent on the aromatic nucleus from the viewpoint of high refractive index. Therefore, the structural formulas (I-1), (II-1), ( Those represented by III-1) are particularly preferred.
- the bicarbazole compound (B) is, for example, the following structural formula (3)
- each R ′ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- a step of obtaining a bicarbazole intermediate (b1) represented by It can be produced by a method through a step of introducing a structural site (hereinafter abbreviated as “step 2”).
- the activated carbon used in the step 1 may be used alone or as a so-called Pd—C catalyst in which a catalyst such as a palladium catalyst is supported on the activated carbon.
- the reaction temperature is not particularly limited, but is preferably within a relatively high temperature range of 140 to 180 ° C. because the reaction proceeds quickly.
- the reaction in Step 1 is preferably performed in an organic solvent, and examples of the organic solvent that can be used here include benzene, xylene, 1,3,5-trimethylbenzene, 1,2-dichlorobenzene, and the like.
- step 1 the following structural formula (5)
- R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a bromine atom, or a chlorine atom.
- purification is performed until the content of the carbazole intermediate (b2) in the reaction product of Step 1 is 15% by mass or less. It is preferable to do.
- Step 2 of introducing a photopolymerizable functional group or a structural site having a photopolymerizable functional group onto the nitrogen atom of the bicarbazole intermediate (b1) has a different reaction method depending on the functional group to be introduced.
- ethylene carbonate is reacted with the terminal hydroxyl group thus produced to react with paratoluenesulfonate chloride, and then in the presence of a basic catalyst.
- a method for producing a vinyl group by carrying out a detosylation reaction is mentioned.
- Step 1 When introducing an acryloyl group, the reaction product of Step 1 is reacted with 3-chloropropionyl chloride to introduce a 3-chloropropionyl group, and then a double bond is formed under a basic catalyst.
- generating is mentioned.
- Step 1 The reaction product is reacted with an alkylene carbonate, further reacted with an alkylene oxide according to a conventional method if necessary to form a hydroxyl group at the terminal, and then reacted with (meth) acrylic acid in the presence of a basic catalyst.
- a basic catalyst e.g.
- the structural site having a photopolymerizable functional group constituting X 1 and X 2 in the structural formula (1) has an oxetanyl group such as a 3-methyloxetanyl-methyl group and a 3-ethyloxetanyl-methyl group.
- a method of reacting the reaction product of Step 1 with 3-chloromethyl-3-alkyloxetane in the presence of a basic catalyst can be mentioned.
- X 1 is a photopolymerizable functional group, a structural moiety having a photopolymerizable functional group, or a hydrogen atom
- R 1 and R 2 are each independently a hydrogen atom or a carbon atom number of 1
- the proportion of the phenylbenzyl (meth) acrylate (A) and the bicarbazole compound (B) has a low viscosity suitable for coating, and Since the effect of high refractive index in the cured product becomes more remarkable, the mass ratio [(A) / (B)] of both is preferably in the range of 10/90 to 99/1. A range of / 70 to 90/10 is particularly preferable.
- the active energy ray-curable composition of the present invention may contain other compound (C) in addition to the phenylbenzyl (meth) acrylate (A) and the bicarbazole compound (B).
- C used here are epoxy (meth) acrylate, fluorene skeleton-containing di (meth) acrylate, (meth) acrylate having a polyoxyalkylene structure, monofunctional (meth) acrylate monomer, polyfunctional type ( And (meth) acrylate monomers.
- the epoxy (meth) acrylate is obtained by reacting an epoxy resin with (meth) acrylic acid or its anhydride, and the epoxy resin is, for example, a dihydric phenol such as hydroquinone or catechol.
- biphenol compound bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compound, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, etc.
- a polyglycidyl ether of a polyether-modified aromatic polyol obtained by ring-opening polymerization with a cyclic ether compound;
- Examples include polyglycidyl ethers of lactone-modified aromatic polyols obtained by polycondensation of the biphenol compounds, bisphenol A, bisphenol B, bisphenol F, bisphenol S, naphthol compounds and lactone compounds such as ⁇ -caprolactone.
- the bisphenol-type epoxy resin or the naphthol compound exhibits a higher refractive index and a cured coating film that exhibits high adhesion to a plastic film substrate even under high temperature and high humidity conditions.
- Polyglycidyl ether is preferable, and the bisphenol-type epoxy resin is particularly preferable.
- those having an epoxy equivalent in the range of 160 to 1,000 g / eq are preferable because a cured product having a higher refractive index and higher hardness can be obtained, and in the range of 165 to 600 g / eq. Is more preferable.
- the fluorene skeleton-containing di (meth) acrylate is specifically represented by the following structural formula (7)
- X is a hydrogen atom or a methyl group
- m and n are each independently an integer of 0 to 5).
- the (meth) acrylate compound having a polyoxyalkylene structure described above has a polyoxyalkylene structure such as a polyethylene glycol chain or a polypropylene glycol chain in its molecular structure.
- a polyoxyalkylene structure such as a polyethylene glycol chain or a polypropylene glycol chain in its molecular structure.
- a polyethylene glycol having 4 to 15 ethylene oxide units for example, a polyethylene glycol having 4 to 15 ethylene oxide units.
- Diacrylate of polyethylene glycol having 4 to 15 ethylene oxide units diacrylate of polypropylene glycol having 4 to 15 propylene oxide units, monoacrylate of polypropylene glycol having 4 to 15 propylene oxide units, ethylene oxide modified glycerol tri Acrylate (EO unit number 3-10), propylene oxide modified glycerol triacrylate (PO unit number 3-10) Of ethylene oxide-modified trimethylolpropane triacrylate (EO unit number 4 to 20), propylene oxide-modified trimethylolpropane triacrylate (PO unit number 4 to 20), ethylene oxide unit 4 to 15 bisphenol ethylene oxide adduct Examples thereof include acrylates and diacrylates of propylene oxide adducts of bisphenol having 4 to 15 propylene oxide units.
- other monofunctional (meth) acrylate monomers include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl ( (Meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylthioethyl (meth) acrylate, o-phenyl Phenoxyethyl (meth) acrylate, naphthoxyethyl (meth) acrylate, naphthylthioethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, g
- Multifunctional (meth) acrylate monomers are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth).
- the blending ratio thereof may be a ratio of 10 to 70% by mass in the polymerization component.
- the blending ratio is preferably 10 to 70% by mass in the polymerization components.
- the active energy ray-curable composition of the present invention further contains a radical polymerization initiator (D).
- a radical polymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy.
- radical polymerization initiators include, for example, “Irgacure-184”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-651”, “Irgacure- -754 “,” Irgacure-784 “,” Irgacure-819 “,” Irgacure-907 “,” Irgacure-1116 “,” Irgacure-1664 “,” Irgacure-1700 “,” Irgacure-1800 “,” Irgacure-1850 “ ”,“ Irgacure-2959 ”,“ Irgacure-4043 ”,“ Darocur-1173 ”(manufactured by Ciba Specialty Chemicals),“ Lucirin TPO ”(manufactured by BASF),“ Kayacure-DETX ”,“ Kayacure-MBP
- the radical polymerization initiator is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition of the present invention in order to exhibit sufficient curability. A range of 1 to 10 parts by mass is more preferable.
- various photosensitizers may be added together with the radical polymerization initiator.
- the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles or other nitrogen-containing compounds, and these can be used alone or in two types. You may use the above together.
- the addition amount of these photosensitizers is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition of the present invention.
- the active energy ray-curable composition of the present invention may contain various other additives as necessary.
- various additives include ultraviolet absorbers, antioxidants, silicone additives, fluorine additives, rheology control agents, defoaming agents, antistatic agents, and antifogging agents.
- the amount added is 0.01 to 100 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition of the present invention as long as the effect of the additive is fully exhibited and ultraviolet curing is not inhibited.
- the range is preferably 40 parts by mass.
- the viscosity of the active energy ray-curable composition of the present invention is such that the active energy ray-curable resin composition can pass through the mold without any defects even under high-speed coating conditions. 1,000 mPa ⁇ s or less is preferable.
- Examples of the active energy rays irradiated when the active energy ray-curable composition of the present invention is cured include electron beams, ultraviolet rays, and visible rays.
- an electron beam is used as the active energy beam, generation of an electron beam such as a Cockloft Walton accelerator, a bandegraph electron accelerator, a resonant transformer accelerator, an insulated core transformer type, a dynamitron type, a linear filament type, and a high frequency type
- the curable composition of the present invention can be cured using an apparatus.
- ultraviolet rays When ultraviolet rays are used as the active energy ray, they can be cured by irradiation with a mercury lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp or a low pressure mercury lamp, a xenon lamp, a carbon arc, a metal height lamp or the like.
- a mercury lamp such as an ultra-high pressure mercury lamp, a high pressure mercury lamp or a low pressure mercury lamp, a xenon lamp, a carbon arc, a metal height lamp or the like.
- the amount of ultraviolet light exposure is preferably in the range of 0.1 to 1000 mJ / cm 2 .
- the cured product of the active energy ray-curable composition of the present invention of the present invention exhibits a high refractive index, is excellent in flexibility, and is less prone to cracking and chipping during cutting.
- plastic lenses such as eyeglass lenses, digital camera lenses, Fresnel lenses, and prism lenses, optical overcoat agents, hard coat agents, antireflection films, optical fibers, optical waveguides, holograms, prisms
- plastic lenses such as eyeglass lenses, digital camera lenses, Fresnel lenses, and prism lenses
- optical overcoat agents such as eyeglass lenses, digital camera lenses, Fresnel lenses, and prism lenses
- optical overcoat agents such as hard coat agents, antireflection films, optical fibers, optical waveguides, holograms, prisms
- various optical materials such as lenses, LED sealing materials, and solar cell coating materials, and among these, it is particularly suitable for plastic lenses such as prism lenses for liquid crystal substrates.
- the prism lens for a liquid crystal substrate has a plurality of fine prism-shaped portions on one side of a sheet-like molded body, and usually the prism surface faces the back side (light source side) of the liquid crystal display element and the element side. Further, a sheet-like lens used so that a light guide sheet is arranged on the back surface thereof, or a sheet-like lens in which the prism lens also functions as the light guide sheet.
- the prism portion of the prism lens preferably has a prism apex angle ⁇ in the range of 70 to 110 ° from the viewpoint of excellent light-collecting properties and improved luminance, and particularly in the range of 75 to 100 °. In particular, the range of 80 to 95 ° is particularly preferable.
- the prism pitch is preferably 100 ⁇ m or less, and particularly preferably in the range of 70 ⁇ m or less from the viewpoint of preventing the generation of moiré patterns on the screen and further improving the definition of the screen.
- the height of the unevenness of the prism is determined by the value of the prism apex angle ⁇ and the prism pitch, but is preferably in the range of 50 ⁇ m or less.
- the sheet thickness of the prism lens is preferably thick from the viewpoint of strength, but optically it is preferably thin in order to suppress light absorption. From the viewpoint of these balances, the sheet thickness is in the range of 50 ⁇ m to 1000 ⁇ m. preferable.
- the method for producing the prism lens using the active energy ray-curable composition of the present invention includes, for example, applying the composition to a molding die such as a mold or a resin die on which a prism pattern is formed, and Examples include a method of superposing a transparent substrate after smoothing the surface, irradiating with an active energy ray from the transparent substrate side, and curing.
- Examples of the transparent base material used here include a plastic base material made of acrylic resin, polycarbonate resin, polyester resin, polystyrene resin, fluororesin, polyimide resin, and glass.
- the prism sheet obtained by the above method can be used as it is, or it can be used in the state of a prism lens alone after peeling the transparent substrate.
- the surface of the transparent base material should be subjected to adhesion improvement treatment such as primer treatment for the purpose of improving the adhesion between the prism lens and the transparent base material. Is preferred.
- the transparent substrate when the transparent substrate is peeled and used, it is preferable to treat the surface of the transparent substrate with silicone or a fluorine-based release agent so that the transparent substrate can be easily peeled off.
- the refractive index of the cured product is preferably 1.5500 or more, and more preferably 1.5700 or more. More preferred.
- Production Example 1 Production of phenylbenzyl acrylate composition (A-1) Synthesis of chloro intermediate Into a 5 L four-necked flask equipped with a stirrer, a condenser, a thermometer, and a hydrogen chloride gas introduction device, 709 g of diphenyl, 276 g of paraformaldehyde, Acetic acid 1381 g and concentrated hydrochloric acid 958 g were charged, and the temperature was raised to 80 ° C. After confirming that the charged solution was 80 ° C., hydrogen chloride gas was introduced into the charged solution at a rate of 20 g / hr using a Kinoshita type glass ball filter.
- the organic layer was concentrated to obtain 995 g of a liquid phenylbenzyl acrylate composition (A-1).
- -Analysis of Phenylbenzyl Acrylate Composition (A-1) The obtained phenylbenzyl acrylate composition (A-1) had a liquid refractive index at 25 ° C of 1.592 and a viscosity of 30 mPa ⁇ s.
- the content of each component contained in 100 parts by mass of the phenylbenzyl acrylate composition (A-1) was measured using a gas chromatogram. As a result, 65.2 parts by mass of phenylbenzyl acrylate and bis (acryloylmethyl) biphenyl were obtained.
- Gas chromatogram analysis conditions for the phenylbenzyl acrylate composition (A-1) are as follows. Equipment: “GC-2010” manufactured by Shimadzu Corporation Column: “Zebron ZB-5” manufactured by Shimadzu Corporation Conditions: He carrier gas, flow rate 1.47 mL / min, column oven 50 ° C., vaporization chamber 300 ° C., temperature rising range 50 ° C. to 300 ° C. (25 ° C./min)
- Production Example 2 Production of bicarbazole compound (B-1) Production of 1,3′-bicarbazole intermediate 300 g (1.75 mol) 1,2,3,4-tetrahydrocarbazole, 300 g activated carbon, 1,2 -2500 g of dichlorobenzene was charged into a reaction vessel and reacted for 36 hours under air bubbling (120 to 150 L / hr) under a temperature condition of 140 to 170 ° C. After confirming that all the raw material 1,2,3,4-tetrahydrocarbazole was consumed by high performance liquid chromatography, the activated carbon was removed by filtration, and the product was concentrated. The concentrate was washed with ethanol at 70 ° C.
- the reaction mixture was cooled to room temperature and 200 ml of toluene was added to dissolve the product.
- bicarbazole compound (B-1)] 9′-Diacryloyl-1,3′-bicarbazole [hereinafter abbreviated as “bicarbazole compound (B-1)]” was obtained.
- a 1H-NMR chart of the bicarbazole compound (B-1) is shown in FIG.
- a sample made into a d6-DMSO solution was measured using an “Avance 400” (400 MHz) manufactured by Bruker.
- Avance 400 400 MHz
- the mass spectrum was measured by “5937 MSD EI” manufactured by Agilent Technologies.
- Examples 1 and 2 and Comparative Examples 1 and 2 The active energy ray-curable composition was adjusted in the following manner, and its viscosity, refractive index, and curability were measured. The results are shown in Table 1. ⁇ Preparation of active energy ray-curable composition Each of the ingredients was blended in the proportions shown in Table 1 to obtain an active energy ray-curable composition. Details of each component in the table are as follows.
- the refractive index of the obtained active energy ray-curable composition was measured using an Abbe refractometer ("NAR-3T" manufactured by Atago Co., Ltd.) at 25 ° C.
- the active energy ray-curable composition prepared in Examples 1 and 2 was coated on a chrome-plated metal plate, and a PET film was laminated thereon to obtain an active energy ray-curable composition layer.
- a laminated body was obtained by irradiating UV light of 500 mJ / cm 2 with a high-pressure mercury lamp from the PET film side.
- the metal plate and the PET film were peeled from the laminate, and it was confirmed that the active energy ray-curable composition was sufficiently cured.
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Abstract
Description
で表されるビカルバゾール化合物(B)とを含有する活性エネルギー線硬化型組成物に関する。
で表されるビカルバゾール化合物(B)とを必須の成分として含有することを特徴とする。これら両化合物を併用することにより、塗工に適した低粘度を有し、かつ、その硬化物における屈折率の高い活性エネルギー線硬化型組成物となる。
で表される通り、カルバゾール構造の1-位炭素原子と3-位炭素原子が結合した構造を有する。このような化合物は結晶化し難く、前記フェニルベンジル(メタ)アクリレート(A)等の他の化合物との相溶性も高い上、硬化物における屈折率が飛躍的に高い特徴を有する。
(式中、R3は炭素原子数2~6のアルキレン基を、R4は水素原子又はメチル基を表し、nは0~10の整数である。)
で表される(メタ)アクリロイル基含有構造部位等のラジカル重合性官能基を持つ構造部位等が挙げられる。
であらわされる1,2,3,4-テトラヒドロカルバゾールを活性炭素の存在下に酸化反応させることにより下記構造式(4)
で表されるビカルバゾール中間体(b1)を得る工程(以下「工程1」と略記する)と、該中間体(b1)の窒素原子上に光重合性官能基又は光重合性官能基を有する構造部位を導入する工程(以下「工程2」と略記する)とを経る方法にて製造することができる。
で表されるカルバゾール中間体(b2)が副生することがあるが、その場合には、工程1の反応生成物中のカルバゾール中間体(b2)の含有率が15質量%以下となるまで精製することが好ましい。
で表されるカルバゾール化合物(B’)が副生することがある。この場合、反応生成物100質量部中のカルバゾール化合物(B’)の含有量は30質量%以下であることが好ましい。
・クロロ中間体の合成
攪拌機、冷却管、温度計、塩化水素ガス導入装置を具備した5L4つ口フラスコに、ジフェニル709g、パラホルムアルデヒド276g、酢酸1381g、濃塩酸958gを仕込み、80℃まで昇温した。仕込み溶液が80℃であることを確認後、木下式ガラスボールフィルターを使って塩化水素ガスを20g/hr速度で仕込み溶液に導入した。仕込み溶液への塩化水素ガスの溶解が飽和であることを確認後、リン酸1061gを1時間かけて滴下し、更に、30時間反応を行った。反応終了後、直ちに反応溶液から下層を取り除き、有機層にトルエン2.3kgを添加し、有機層を400gの12.5%水酸化ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、蒸留水で洗浄した。有機層を留去後、クロロ中間体を白色固体として908g得た。
・アクリレート化
上記で得られた中間体908gを反応溶媒であるジメチルホルムアミド1603gに溶解し、炭酸カリウム372gおよびメトキノンを全量に対して300ppmになるように添加した。中間体溶液を40℃に昇温後、アクリル酸323gを1.5時間で中間体溶液に滴下した。滴下終了後、2時間かけて80℃まで昇温し、80℃にて3時間加熱撹拌した。得られた溶液に水3.4kgおよびトルエン1.8kgを添加し抽出を行った後、有機層を水層が中性になるまで洗浄した。有機層を濃縮して液状のフェニルベンジルアクリレート組成物(A-1)を995g得た。
・フェニルベンジルアクリレート組成物(A-1)の分析
得られたフェニルベンジルアクリレート組成物(A-1)の25℃における液屈折率は1.592であり、粘度は30mPa・sであった。フェニルベンジルアクリレート組成物(A-1)100質量部中に含まれる各成分の含有量を、ガスクロマトグラムを用いて測定したところ、フェニルベンジルアクリレートが65.2質量部、ビス(アクリロイルメチル)ビフェニルが18.6質量部、ビフェニル構造がメチレンを介して結節された分子構造を有するビフェニル化合物が2.3質量部、ビフェニルが5.8質量部含まれており、残りの8.1質量部にはビフェニル以外の未反応原料等が含まれていた。また、フェニルベンジルアクリレートの異性体の質量比(モル比も同等)[〔オルトフェニルベンジルアクリレート〕/〔メタフェニルベンジルアクリレート〕/〔パラフェニルベンジルアクリレート〕]は20/1/79であった。
機器:島津社製「GC-2010」
カラム:島津社製「Zebron ZB-5」
条件:Heキャリアガス、流量1.47mL/min、カラムオーブン50℃、気化室300℃、昇温範囲50℃から300℃(25℃/min)
・1,3’-ビカルバゾール中間体の製造
1,2,3,4-テトラヒドロカルバゾール300g(1.75モル)、活性炭素300g、1,2-ジクロロベンゼン2500gを反応容器に仕込み、140~170℃の温度条件下、エアーバブリング(120~150L/hr)を行いながら36時間反応させた。高速液体クロマトグラフィーにて原料の1,2,3,4-テトラヒドロカルバゾールが全て消費されていることを確認した後、ろ過により活性炭素を除去し、生成物を濃縮した。濃縮物を70℃で3時間かけてエタノールで洗浄し、懸濁液をろ過、乾燥して粗生成物を得た。粗成生物をカラムクロマトフラフィーで精製した後、室温で3時間かけてジクロロメタンで洗浄し、純度90質量%の1,3’-ビカルバゾール中間体8.7gを得た(ここで、残余の10質量%はカルバゾールであった)。
・アクリレート化
先で得た純度90質量%の1,3’-ビカルバゾール中間体5.0g(15mmol)を、3-クロロプロピオンニルクロリド45.4g(358mmol)に懸濁し、発生する塩化水素ガスを窒素気流で排出しながら130℃、8時間反応させた。反応混合物を室温に冷却し、トルエン200mlのトルエンを加えて生成物を溶解させた。水で2回、飽和炭酸水素ナトリウム溶液で1回、飽和塩化ナトリウム溶液で1回の順で洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を減圧留去後、シリカゲルカラムクロマトグラフィー(n-ヘプタン:酢酸エチル=9:1)で精製し、6.5gの白色結晶の9,9’-ビス(3-クロロプロピオニル)-1,3’-ビカルバゾールを得た。
次いで、300mlの三口フラスコに、6.0gの9,9’-ビス(3-クロロプロピオニル)-1,3’-ビカルバゾールと0.2gの4-メトキシフェノールを、60mlのトルエンに溶解した。この溶液に、2.37gのトリエチルアミン(23.4mmol)を撹拌しながら添加し、その後60℃で4時間反応させた。反応溶液を室温まで冷却し、200mlのトルエンを加え、飽和塩化ナトリウム水で1回、2%塩酸で1回、飽和炭酸水素ナトリウム水で1回、飽和塩化ナトリウム水で1回の順で洗浄した。無水硫酸マグネシウムで乾燥後、溶媒を減圧留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィー(n-ヘプタン:酢酸エチル=9:1)で精製し、5.1gの白色結晶の9,9’-ジアクリロイル-1,3’-ビカルバゾール[以下「ビカルバゾール化合物(B-1)」と略記する]を得た。ビカルバゾール化合物(B-1)の1H-NMRのチャートを図1に示す。1H-NMRはd6-DMSO溶液にしたサンプルを、Bruker社製「Avance400」(400MHz)を用いて測定した。ビカルバゾール化合物(B-1)のマススペクトルを測定した結果、m/z440,386,332のピークを確認した。マススペクトルはAgilent Technologies社製「5937 MSD EI」にて測定した。
以下の要領で活性エネルギー線硬化型組成物を調整し、その粘度と屈折率、及び硬化性を測定した。結果を表1に示す。
◆活性エネルギー線硬化型組成物の調整
各配合成分を表1に示す割合で配合し、活性エネルギー線硬化型組成物を得た。表中の各成分の詳細は以下の通り。
PBA(A-1):製造例1で得たフェニルベンジルアクリレート組成物(A-1)
VBIC(B-1):製造例2で得たビカルバゾール化合物(B-1)
開始剤:チバスペシャルティーケミカルズ社製「ルシリンTPO」
フルオレン:新中村工業株式会社製「A-BPEF」 9,9-ビス[4-(2-アクリロイルオキシエトキシ)フェニル]フルオレン
得られた活性エネルギー線硬化型組成物の粘度を、E型回転粘度計(東機産業株式会社製「RE80U」)を使用し、25℃条件下で測定した。
得られた活性エネルギー線硬化型組成物の屈折率を、アッべ屈折率計(アタゴ社製「NAR-3T」)を使用し、25℃条件化で測定した。
実施例1、2で調整した活性エネルギー線硬化型組成物について、これをクロムメッキ処理金属板上に塗布し、その上からPETフィルムを重ね、活性エネルギー線硬化型組成物層が50μmとなるように調整した。PETフィルム側から高圧水銀灯により500mJ/cm2の紫外線を照射し、積層体を得た。積層体から金属板及びPETフィルムを剥離し、活性エネルギー線硬化型組成物が十分に硬化していることを確認した。
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JP2006520409A (ja) * | 2003-02-12 | 2006-09-07 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | カルバゾール化合物及び有機電界発光デバイスにおけるこのような化合物の使用 |
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WO2015165089A1 (en) * | 2014-04-30 | 2015-11-05 | Dic Corporation | Bicarbazole compound, photo-curable composition, cured produc thereof, curable composition for plastic lens, and plastic lens |
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- 2016-10-06 KR KR1020187012524A patent/KR20180070599A/ko not_active Application Discontinuation
- 2016-10-20 TW TW105133814A patent/TWI722029B/zh active
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KR20180070599A (ko) | 2018-06-26 |
JP6187846B1 (ja) | 2017-08-30 |
JPWO2017068988A1 (ja) | 2017-10-19 |
US10921490B2 (en) | 2021-02-16 |
US20180306947A1 (en) | 2018-10-25 |
TWI722029B (zh) | 2021-03-21 |
TW201728652A (zh) | 2017-08-16 |
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