WO2023190508A1 - Optical member, material for forming optical member and method for manufacturing same, and method for manufacturing optical member - Google Patents
Optical member, material for forming optical member and method for manufacturing same, and method for manufacturing optical member Download PDFInfo
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- WO2023190508A1 WO2023190508A1 PCT/JP2023/012497 JP2023012497W WO2023190508A1 WO 2023190508 A1 WO2023190508 A1 WO 2023190508A1 JP 2023012497 W JP2023012497 W JP 2023012497W WO 2023190508 A1 WO2023190508 A1 WO 2023190508A1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
-
- 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
Definitions
- the present invention relates to an optical member, an optical member forming material, a method for manufacturing the same, and a method for manufacturing the optical member.
- High refractive index resins are used for various optical members such as lenses and touch panel films.
- resins using monomers having a fluorene skeleton are known (for example, Patent Documents 1 and 2).
- An object of the present invention is to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same. do.
- An optical member including a structure represented by the following formula (i).
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4
- (e+g) is 1 to 5
- (f+h) is 1 to 5.
- R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4,
- e+g) is 1 to 5
- (f+h) is 1 to 5.
- R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
- the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
- the resin is a polycarbonate resin or a polyester resin.
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4,
- e+g) is 1 to 5
- (f+h) is 1 to 5.
- X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom
- (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group
- R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4,
- e+g) is 1 to 5
- (f+h) is 1 to 5.
- R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4,
- e+g) is 1 to 5
- (f+h) is 1 to 5.
- a method for producing an optical member forming material comprising a step of producing a compound.
- a method for producing an optical member comprising molding the optical member forming material according to any one of [6] to [8].
- a method for producing an optical member which comprises curing the optical member forming material according to [9].
- the present invention it is possible to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same.
- the optical member of the present invention includes a structure represented by the following formula (i) (hereinafter also referred to as “structure (i)").
- R 1 is a hydrogen atom or an aryl group
- a is an integer from 0 to 5
- b is an integer from 0 to 4
- R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different
- c and d are each independently an integer of 0 to 6
- R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5.
- R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
- Examples of the aryl group for R 1 include a phenyl group.
- a phenyl group is preferable from the viewpoint of increasing the refractive index, and a hydrogen atom is preferable from the viewpoint of ease of reactivity when synthesizing the present compound.
- a is an integer from 0 to 5, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
- b is an integer from 0 to 4, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
- the substituent for R 2 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, a cyano group, an acetyl group, and a halogen atom.
- c and d are each independently an integer of 0 to 6. In one preferred embodiment, c and d are 0. Structure (i) is typically derived from compound (1) described below. In compound (1), when c is 0, the terminal OH of HO-(R 3 O) c - becomes a phenolic hydroxyl group by bonding to the benzene ring to which HO-(R 3 O) c - is bonded. , -(OR 3 ) d The same applies to the terminal OH of -OH. In this case, when compound (1) is used as a raw material to produce polycarbonate resins, polyester resins, and other compounds, they tend to have excellent reactivity. In another preferred embodiment, c and d are integers of 1 or more.
- the alkylene group in R 3 has, for example, 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms.
- the alkylene group may be linear or branched. Specific examples of the alkylene group include ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, and hexylene group.
- e and f are each independently an integer of 1 to 5
- g and h are each independently an integer of 0 to 4
- (e+g) is 1 to 5
- (f+h) is 1 to 5.
- e and f are particularly preferably 1 when the compound (1) is used as a raw material for polycarbonate resin or polyester resin.
- Compound (1) can be used as it is as a curing agent for epoxy resins, or the hydroxyl group of compound (1) can be replaced with a group containing a polymerizable functional group or a reactive functional group, and it can be incorporated into a curable composition. You can also do that.
- e and f each independently range from 1 to 4, since the crosslinking density increases when the curable composition is cured, thereby increasing the mechanical strength and heat resistance of the cured product.
- g and h are each independently preferably an integer of 1 to 2, and 1 is particularly preferred.
- the substituent for R 4 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, an acetyl group, a halogen atom, and -(OR 3 ) k OH.
- R3 is the same as above.
- k is an integer from 0 to 6.
- R 4 is preferably an alkyl group from the viewpoint of ease of raw material procurement.
- the number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 2.
- the alkyl group may be linear or branched.
- e and f are 1, g and h are each independently an integer of 1 to 2, and R It is preferred that 4 is an alkyl group.
- R 1 , a, b, c, d, and R 3 are the same as described above.
- e and f are each independently an integer of 1 to 4;
- g and h are each independently an integer of 1 to 2, and
- R 4 is preferably an alkyl group.
- optical member (1) One embodiment of the optical member of the present invention is a resin (hereinafter also referred to as "resin A”) having a structural unit based on a compound represented by the following formula (1) (hereinafter also referred to as “compound (1)”). ) (hereinafter also referred to as “optical member (1)”).
- the structural unit based on compound (1) includes the structure (i) described above.
- R 1 , a, b, R 2 , c, d, R 3 , e, f, g, h and R 4 are each as described above.
- Examples of the resin A include resins containing a polyvalent hydroxy compound as a monomer component, in which at least a portion of the polyvalent hydroxy compound is compound (1).
- a polyhydric hydroxy compound is a compound having two or more hydroxyl groups.
- polycarbonate resins examples include polycarbonate resins having a structural unit represented by the following formula (a1) (hereinafter also referred to as "constituent unit (a1)").
- the polycarbonate resin may have one or more types of structural units (a1).
- the polycarbonate resin may further have other structural units other than the structural unit (a1).
- Examples of other structural units include structural units based on polyvalent hydroxy compounds other than compound (1) (hereinafter also referred to as "structural units (a2)").
- the structural unit (a2) is represented by the following formula (a2).
- R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound.
- Other polyhydric hydroxy compounds are typically dihydroxy compounds. There are no particular limitations on the other polyhydric hydroxy compounds, and those known as monomer components of polycarbonate resins can be used. Examples of other polyhydric hydroxy compounds include aromatic polyhydroxy compounds such as aromatic dihydroxy compounds, and aliphatic polyhydroxy compounds such as aliphatic dihydroxy compounds.
- aromatic dihydroxy compounds include phenolic compounds such as hydroquinone and resorcinol; bisphenol compounds such as bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol C, bisphenol E, bisphenol S, bisphenol Z, bisphenol CDE, and bisphenol fluorene; Examples include bisnaphtholfluorene and 4,4'-dihydroxybiphenyl.
- the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.
- the polycarbonate resin may have one or more structural units (a2).
- polyester resin Another example of a resin containing a polyhydric hydroxy compound as a monomer component is a polyester resin.
- polyester resins using compound (1) as a monomer component include polyester resins having a structural unit represented by the following formula (b1) (hereinafter also referred to as "constituent unit (b1)").
- R 5 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
- the dicarboxylic acid is not particularly limited, and those known as monomer components of polyester resins can be used.
- Examples of dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid.
- the polyester resin may have one or more types of structural units (b1).
- the polyester resin may further have other structural units other than the structural unit (b1).
- Examples of other structural units include a structural unit represented by the following formula (b2) (hereinafter also referred to as "structural unit (b2)").
- R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound
- R 7 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
- examples of other polyhydric hydroxy compounds and dicarboxylic acids include those mentioned above.
- the polyester resin may have one or more types of structural units (b2).
- the optical member (1) may further contain other components other than resin A, if necessary, within a range that does not impair the effects of the present invention.
- other components include colorants, inorganic fillers, organic fillers, antioxidants, and other various additives.
- one kind may be used alone or two or more kinds may be used in combination.
- the optical member (1) can be manufactured, for example, by molding an optical member forming material containing resin A (hereinafter also referred to as "optical member forming material (1)").
- the optical member forming material (1) may further contain other components than the resin A, if necessary, within a range that does not impair the effects of the present invention. Other components include those mentioned above.
- the method for manufacturing the optical member forming material (1) will be explained in detail later.
- thermoplastic resins As a molding method for the optical member forming material (1), known methods for molding thermoplastic resins can be used, such as injection molding, transfer molding, extrusion molding, blow molding, vacuum molding, compression molding, etc. Can be mentioned.
- Optical member forming material (1) can be produced, for example, by producing resin A using compound (1) as at least part of the monomer components, and mixing other components as necessary. Resin A can be manufactured by a known manufacturing method except for using compound (1) as at least a part of the monomer components.
- compound (1) Before producing resin A, compound (1) may be produced.
- Compound (1) can be produced, for example, by a production method including Step A below.
- Step A A biphenyl compound represented by the following formula (1a), a hydroxy compound represented by the following formula (1b), and a hydroxy compound represented by the following formula (1c) are reacted to form the following formula (1- A step of obtaining the compound represented by 1) (hereinafter also referred to as "compound (1-1)"). If necessary, after step A, the following step B is performed.
- Step B A step of adding one or more oxyalkylene groups to the hydroxyl group of compound (1-1) obtained in Step A.
- R 1 , a, b, and R 2 are each as described above.
- the biphenyl compound include 4-biphenylaldehyde, 4-bromo-4'-biphenylaldehyde, 4-benzoylbiphenyl, and 4-bromo-4'-benzoylbiphenyl. These biphenyl compounds may be used alone or in combination of two or more. Among these, 4-biphenylaldehyde is preferred in terms of ease of procurement of raw materials. 4-Bromo-4'-biphenylaldehyde is preferred because the compound (1) produced can exhibit a higher refractive index by having a bromine atom.
- Hydroxy compound In formulas (1b) and (1c), c, d, e, f, g, h, R 3 and R 4 are each as described above.
- the hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) may be the same or different.
- the hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) will be collectively referred to as simply "hydroxy compound.”
- Hydroxy compounds include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-phenylphenol, p-walnutphenol, p-nonylphenol, bisphenol A, bisphenol F, bisphenol B, and bisphenol AP.
- the molar ratio between the biphenyl compound and the hydroxy compound (biphenyl compound/hydroxy compound) when the biphenyl compound and the hydroxy compound are reacted is preferably 0.01 to 1.00, more preferably 0.05 to 0.50. If the molar ratio of biphenyl compound/hydroxy compound is 1.00 or less, a compound (1-1) in which two molecules of hydroxy compound are added to one molecule of biphenyl compound tends to be produced as a main component. When the biphenyl compound/hydroxy compound molar ratio exceeds 1.00, the biphenyl compound and the hydroxy compound tend to be added alternately, which may result in a low yield of compound (1-1).
- a biphenyl compound and a hydroxy compound are reacted in the presence of an acid catalyst.
- an acid catalyst By using an acid catalyst, the reaction between the biphenyl compound and the hydroxy compound proceeds easily.
- acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, acetic acid, citric acid, tartaric acid, benzoic acid, and paratoluenesulfonic acid; and organic acid salts such as zinc acetate and zinc borate. ;
- Examples include ion exchange resins having sulfone groups and carboxylic acid groups.
- oxalic acid, hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid are useful because they suppress the generation of byproducts due to side reactions and at the same time, they can be easily decatalyzed by washing with water after the reaction.
- These acid catalysts may be used alone or in combination of two or more. The amount of the acid catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
- a co-catalyst When reacting a biphenyl compound and a hydroxy compound, a co-catalyst may be used if necessary.
- the co-catalyst include mercaptans such as methyl mercaptan, ethyl mercaptan, normal propyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, stearyl mercaptan, and dodecyl mercaptan. These promoters may be used alone or in combination of two or more.
- the amount of co-catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
- Step A can be carried out in the same manner as the usual method for producing novolac type phenolic resin.
- a product containing compound (1-1) can be produced.
- the solvent include water such as ion-exchanged water; organic solvents such as diethyl ether, cyclopentyl methyl ether, methanol, ethanol, benzene, toluene, and xylene. These may be used alone or in combination of two or more.
- the reaction temperature is, for example, 10 to 150°C.
- the reaction time is, for example, 0.5 to 48 hours. After the reaction is completed, treatments such as extraction, water washing, concentration, and recrystallization may be performed as necessary.
- a method for adding one or more oxyalkylene groups known methods can be used. For example, a method of reacting the compound (1-1) with an alkylene oxide such as ethylene oxide may be mentioned.
- optical member (2) Another embodiment of the optical member of the present invention is a curable composition (hereinafter referred to as "optical member forming material”) containing a compound represented by the following formula (2) (hereinafter also referred to as “compound (2)”).
- Examples include optical members (hereinafter also referred to as “optical members (2)”) containing a cured product of (also referred to as “optical members (2)”).
- the cured product has a structural unit based on compound (2).
- the structural unit based on compound (2) includes the structure (i) described above.
- R 1 , a, b, R 2 , c, d, R 3 , e, f, g, h and R 4 are each as described above.
- X is a monovalent group containing a polymerizable functional group or a reactive functional group (hereinafter also referred to as "group (x)"), or a hydrogen atom, and (e+f) X's may be the same or different. Often, at least one of the (e+f) X's is a group (x). Since compound (2) has one or more polymerizable functional groups or reactive functional groups, it can be cured alone or with a curing agent.
- the polymerizable functional group in group (x) is not particularly limited as long as it is polymerizable, and examples include (meth)acryloyl groups.
- a (meth)acryloyl group means an acryloyl group or a methacryloyl group.
- the reactive functional group in the group (x) include an epoxy group, an acid anhydride group, and an amino group.
- the number of polymerizable functional groups or reactive functional groups possessed by the group (x) may be one or two or more, but typically it is one.
- the polymerizable functional group or reactive functional group may be bonded directly to the oxygen atom adjacent to X, or may be bonded via a linking group.
- Examples of the group (x) include a group represented by -X 2 -X 1 .
- X 1 is a polymerizable functional group or a reactive functional group
- X 2 is a single bond or a divalent linking group.
- the divalent linking group in X 2 is, for example, a divalent hydrocarbon group that may have a substituent, a terminal of a divalent hydrocarbon group that may have a substituent, or/and a carbon
- Examples include groups containing etheric oxygen atoms between atoms.
- Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, an arylene group, and a group consisting of a combination of two or more thereof.
- Examples of the alkylene group include those similar to the alkylene group for R3 .
- Examples of the substituent that the alkylene group may have include a hydroxyl group, a cyano group, and a halogen atom.
- the number of carbon atoms in the cycloalkylene group is, for example, 6 to 8.
- Examples of the substituent that the cycloalkylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom.
- Examples of the arylene group include phenylene group, naphthylene group, phenanthrylene group, anthrylene group, and 4,4'-biphenyl-diyl group.
- substituents that the arylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom.
- X 2 is preferably one having a hydroxyl group as a substituent. If X 2 has a hydroxyl group, the cured product using compound (2) tends to have better heat resistance and mechanical strength. This is thought to be because the presence of hydroxyl groups provides intermolecular force due to hydrogen bonds, increasing the cohesive force of molecules. Moreover, this hydrogen bond also contributes to improving the adhesion to inorganic or organic substances (for example, films, lenses, etc.) such as glass and polyester.
- inorganic or organic substances for example, films, lenses, etc.
- Ph is a phenylene group
- Y1 is a glycidyl group
- R is a hydrogen atom or
- a 2-hydroxy-3-(meth)acryloyloxypropyl group is preferred since the cured product has excellent heat resistance and mechanical strength and is useful as an optical member.
- the optical member forming material (2) may further contain other components other than the compound (2), if necessary, within a range that does not impair the effects of the present invention.
- Other components include, for example, a compound having a polymerizable functional group or a reactive functional group other than compound (2), a curing agent (crosslinking agent, polymerization initiator, etc.), a curing accelerator, a solvent, a coloring agent, an inorganic filler. additives, organic fillers, antioxidants, and other various additives.
- a curing agent crosslinking agent, polymerization initiator, etc.
- a curing accelerator curing accelerator
- solvent solvent
- coloring agent an inorganic filler
- additives organic fillers, antioxidants, and other various additives.
- one kind may be used alone or two or more kinds may be used in combination.
- the optical member forming material (2) preferably contains a polymerization initiator (photopolymerization initiator, thermal polymerization initiator, etc.).
- the optical member forming material (2) preferably contains a crosslinking agent having two or more functional groups that can react with the reactive functional group of the group (x).
- the reactive functional group is an epoxy group
- examples of the functional group that can react with the epoxy group include an amino group, an acid anhydride group, and a hydroxyl group.
- examples of the functional group that can react with the acid anhydride group include an amino group and a hydroxyl group.
- the reactive functional group is an amino group
- examples of the functional group that can react with the amino group include acid anhydride groups.
- Examples of the crosslinking agent used when the group (x) has an acid anhydride group include diamine.
- polyimide is produced by the reaction between compound (2) and diamine.
- Examples of diamines include 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, diamine compounds, diethylene glycol bis(3-aminopropyl) Examples include ether and 9,9'-bis(4-aminophenyl)fluorene.
- One type of diamine may be used alone or two or more types may be used in combination.
- the optical member (2) can be manufactured by curing the optical member forming material (2).
- the optical member forming material (2) may be manufactured before the optical member forming material (2) is cured.
- the method for manufacturing the optical member forming material (2) will be explained in detail later.
- the method for curing the optical member forming material (2) is not particularly limited, and known methods can be applied depending on the type of polymerizable functional group or reactive functional group that the group (x) has. For example, when the group (x) has a polymerizable functional group, by applying light or heat to the optical member forming material (2), the compound (2) etc. can be polymerized to form a cured product. When curing the optical member forming material (2), the optical member forming material (2) may be molded into the shape of the desired optical member. After curing the optical member forming material (2), the cured product may be molded into the shape of the desired optical member.
- Optical member forming material (2) can be manufactured, for example, by manufacturing compound (2) and mixing other components as necessary.
- Compound (2) can be produced, for example, by a production method including Step C below.
- Step C A step of adding group (x) to at least a portion of the OH of compound (1), which is a compound in which all OX in formula (2) are OH.
- Step C can be carried out using a known method depending on the structure of group (x).
- group (x) is a glycidyl group
- a method in which the OH of compound (1) is reacted with epihalohydrin (e.g., epichlorohydrin) can be used.
- epihalohydrin e.g., epichlorohydrin
- Group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1
- (n+1) mol of bisphenol A type epoxy compound (HO-Ph-C(CH 3 ) 2 -Ph-O-Y 1 ) is reacted with respect to 1 mol of OH.
- the group (x) is a (meth)acryloyl group
- a method of reacting the OH of compound (1) with (meth)acrylic acid, (meth)acrylic anhydride or (meth)acrylic acid halide hereinafter referred to as " (also referred to as "Method 2").
- the group (x) is a 2-(meth)acryloyloxy-2-hydroxyethyl group
- a compound in which the group (x) is a glycidyl group is obtained by the above method 1, and (meth)acrylic is added to the glycidyl group of this compound.
- Method 3 A method of reacting an acid, (meth)acrylic anhydride, or (meth)acrylic acid halide (hereinafter also referred to as "Method 3") can be mentioned.
- the group (x) instead of obtaining a compound in which the group (x) is a glycidyl group, the group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 may be obtained.
- the molar ratio of epihalohydrin to OH of compound (1) is the same molar ratio as when producing bisphenol A type epoxy resin, which is the most common epoxy resin, from bisphenol A and epichlorohydrin. It may be a ratio.
- the OH/epichlorohydrin ratio is preferably 0.02 to 0.33, more preferably 0.10 to 0.20.
- the optical member of the present invention described above has the structure (i), it exhibits a high refractive index (for example, a refractive index of 1.62 to 1.78).
- a high refractive index for example, a refractive index of 1.62 to 1.78.
- One way to increase the polarization of the entire molecule is to increase the number of freely movable conjugated ⁇ electrons.
- the 12 ⁇ electrons present in the two benzene rings resonate over a wide range of the entire biphenyl moiety.
- optical member of the present invention examples include microlenses for CMOS image sensors, index matching materials for touch panels, black matrices for liquid crystals, optical adhesives, transparent polyimides, transparent electrodes for LEDs, and the like.
- ⁇ Measuring method ⁇ ⁇ NMR measurement> A 7.7% d-dimethylsulfoxide (DMSO) solution of the sample (compound of each example) was prepared, and 1 H-NMR and 13 C-NMR were measured. Tetramethylsilane was used as an internal standard. Equipment used: JEOL RESONANCE ECZ-500R
- Example 1 In a 200 mL four-neck flask equipped with a stirrer, thermometer, and Allene condenser, 64.86 g (0.60 mol) of o-cresol, 10.93 g (0.06 mol) of 4-biphenylaldehyde, and ions as a reaction solvent were placed. 10.93 g of exchanged water was charged and stirred. 0.559 g (0.0028 mol) of dodecyl mercaptan was added thereto, and the reaction solution was heated to 55°C. When the temperature reached 55° C., 18.42 g of 35% hydrochloric acid was added over 8 minutes. Upon addition of the catalyst, the color of the reaction solution changed from pale yellow to pale pink.
- the needle-shaped crystals were suction-filtered, and the crystals on the Nutsche were washed with an appropriate amount of isopropyl alcohol and ion-exchanged water, resulting in a pale orange residue. By air drying this, 13.01 g of pale orange powder was obtained.
- This powder was found by GPC to be a powder whose main component was o-cresol which had not reacted with the target compound.
- 13.0 g of isopropyl alcohol and 13.0 g of ion-exchanged water were added to this powder, and the mixture was heated and dissolved to perform recrystallization. When this was allowed to cool to room temperature and left still, pale orange crystals were precipitated.
- Example 2 The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of p-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel.
- This ether layer was washed twice with 173.0 g of ion-exchanged water, and the washed ether solution was subjected to vacuum distillation to remove ether, thereby obtaining 80.61 g of a slurry. 40.3 g of isopropyl alcohol was added to this slurry and refluxed to dissolve the slurry. 40.3 g of ion-exchanged water was added thereto and allowed to cool. The powder precipitated by cooling was separated by suction filtration (filter paper: ADVANTEC5C) using a nutsche and a suction bottle to obtain 52.37 g of a pale yellow powdery crude product.
- 13C -NMR (500MHz, DMSO-d 6 ): ⁇ 41.2, 102.5, 105.5, 121.3, 126.2, 126.5, 129.0, 129.5, 130.2 , 137.2, 140.3, 145.0, 155.5, 156.4.
- Comparative example 2 As a compound of Comparative Example 2, commercially available bisphenol A (manufactured by Mitsui Chemicals, Inc.) shown in the following formula (14) was prepared.
- Example 3 The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of m-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel.
- Example 4 The reaction was carried out in the same manner as in Example 3, except that m-cresol was replaced with 64.86 g (0.60 mol) of MP-cresol (a mixture of m-cresol and p-cresol, "M-301" manufactured by Sumitomo Chemical Co., Ltd.). After cooling the reaction solution, it was neutralized with a 30% sodium hydroxide solution, extracted with cyclopentyl methyl ether, and washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 77.0 g of a brown concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted MP-cresol.
- MP-cresol a mixture of m-cresol and p-cresol, "M-301" manufactured by Sumitomo Chemical Co., Ltd.
- Example 5 The reaction was carried out in the same manner as in Example 1, except that o-cresol was changed to 56.46 g (0.60 mol) of phenol. After cooling the reaction solution, it was neutralized with 30% sodium hydroxide solution and extracted with cyclopentyl methyl ether. , and further washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 32.6 g of a reddish-orange concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted phenol. This residue was heated and dissolved by adding 3.2 g of isopropyl alcohol and 3.2 g of ion-exchanged water, and recrystallized.
- Tables 1 and 2 show the concentration and refractive index of the solutions used to measure the refractive index of the compounds of Examples 1 and 5 and Comparative Examples 1 and 2, the refractive index determined based on them, and the solubility (1 ) and solubility (2) evaluation results are shown.
- the refractive index is a value rounded to the third decimal place. Values to the fourth decimal place are also written in parentheses.
- the compound of Comparative Example 1 had a higher refractive index than the compound of Comparative Example 2, which is generally used as a raw material for polycarbonate resin, it was inferior in solvent solubility.
- the compounds of Examples 1 to 5 had a higher refractive index than the compound of Comparative Example 2, and had excellent solvent solubility.
- the present invention it is possible to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same.
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Abstract
An optical member pertaining to an embodiment of the present invention includes a structure represented by formula (i). In the formula: R1 is a hydrogen atom or an aryl group; a is an integer of 0 to 5; b is an integer of 0 to 4; R2 is a substituent; when (a+b) is 2 or greater, (a+b) R2 groups may be the same or different; c and d are each independently an integer of 0 to 6; R3 is an alkylene group; when (c+d) is 2 or greater, (c+d) R3 groups may be the same or different; e and f are each independently an integer of 1 to 5; g and h are each independently an integer of 0 to 4; (e+g) is 1 to 5; (f+h) is 1 to 5; R4 is a substituent; and when (g+h) is 2 or greater, (g+h) R4 groups may be the same or different.
Description
本発明は、光学部材、光学部材形成材料、その製造方法および光学部材の製造方法に関する。
本願は、２０２２年３月３１日に、日本に出願された特願２０２２－０５９５９６号、および２０２３年３月１７日に、日本に出願された特願２０２３－０４３５７０号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an optical member, an optical member forming material, a method for manufacturing the same, and a method for manufacturing the optical member.
This application claims priority based on Japanese Patent Application No. 2022-059596 filed in Japan on March 31, 2022 and Japanese Patent Application No. 2023-043570 filed in Japan on March 17, 2023. , the contents of which are incorporated herein.
本願は、２０２２年３月３１日に、日本に出願された特願２０２２－０５９５９６号、および２０２３年３月１７日に、日本に出願された特願２０２３－０４３５７０号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to an optical member, an optical member forming material, a method for manufacturing the same, and a method for manufacturing the optical member.
This application claims priority based on Japanese Patent Application No. 2022-059596 filed in Japan on March 31, 2022 and Japanese Patent Application No. 2023-043570 filed in Japan on March 17, 2023. , the contents of which are incorporated herein.
高屈折率樹脂は、レンズ、タッチパネル用フィルム等の各種の光学部材に用いられる。高屈折率樹脂としては、フルオレン骨格を有するモノマーを用いた樹脂が知られている（例えば特許文献１～２）。
High refractive index resins are used for various optical members such as lenses and touch panel films. As high refractive index resins, resins using monomers having a fluorene skeleton are known (for example, Patent Documents 1 and 2).
しかし、上述のフルオレン骨格を有するモノマーは、溶剤溶解性が低い等の実用上の問題がある。そこで、フルオレン骨格以外の新規な骨格を持つ光学部材が求められる。
However, the above-mentioned monomers having a fluorene skeleton have practical problems such as low solvent solubility. Therefore, there is a need for an optical member having a new skeleton other than the fluorene skeleton.
本発明は、新規な骨格を持つ高屈折率の光学部材およびその製造方法、ならびに新規な骨格を持つ高屈折率の光学部材が得られる光学部材形成材料およびその製造方法を提供することを目的とする。
An object of the present invention is to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same. do.
本発明は以下の態様を有する。
［１］下記式（ｉ）で表される構造を含む、光学部材。
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［２］下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材。
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［３］前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である［２］に記載の光学部材。
［４］前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である［２］に記載の光学部材。
［５］下記式（２）で表される化合物を含む硬化性組成物の硬化物を含む、光学部材。
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［６］下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材形成材料。
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［７］前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である［６］に記載の光学部材形成材料。
［８］前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である［６］に記載の光学部材形成材料。
［９］下記式（２）で表される化合物を含む硬化性組成物である、光学部材形成材料。
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［１０］［６］～［８］のいずれかに記載の光学部材形成材料を製造する方法であって、
モノマー成分の少なくとも一部に前記式（１）で表される化合物を用いて前記樹脂を製造する工程を有する、光学部材形成材料の製造方法。
［１１］［９］に記載の光学部材形成材料を製造する方法であって、
前記式（２）中のＯＸが全てＯＨである化合物の前記ＯＨの少なくとも一部に、重合性官能基または反応性官能基を含む１価基を付加して前記式（２）で表される化合物を製造する工程を有する、光学部材形成材料の製造方法。
［１２］［６］～［８］のいずれかに記載の光学部材形成材料を成形する、光学部材の製造方法。
［１３］［９］に記載の光学部材形成材料を硬化する、光学部材の製造方法。 The present invention has the following aspects.
[1] An optical member including a structure represented by the following formula (i).
Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[2] An optical member containing a resin having a structural unit based on a compound represented by the following formula (1).
Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[3] The optical member according to [2], wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
[4] The optical member according to [2], wherein the resin is a polycarbonate resin or a polyester resin.
[5] An optical member containing a cured product of a curable composition containing a compound represented by the following formula (2).
Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[6] An optical member forming material containing a resin having a structural unit based on a compound represented by the following formula (1).
Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[7] The optical member forming material according to [6], wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
[8] The optical member forming material according to [6], wherein the resin is a polycarbonate resin or a polyester resin.
[9] An optical member forming material which is a curable composition containing a compound represented by the following formula (2).
Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[10] A method for producing the optical member forming material according to any one of [6] to [8], comprising:
A method for producing an optical member forming material, comprising the step of producing the resin using a compound represented by the formula (1) as at least a part of the monomer components.
[11] A method for manufacturing the optical member forming material according to [9], comprising:
A monovalent group containing a polymerizable functional group or a reactive functional group is added to at least a portion of the OH of a compound in which all OX in the formula (2) are OH, and the compound is represented by the formula (2). A method for producing an optical member forming material, comprising a step of producing a compound.
[12] A method for producing an optical member, comprising molding the optical member forming material according to any one of [6] to [8].
[13] A method for producing an optical member, which comprises curing the optical member forming material according to [9].
［１］下記式（ｉ）で表される構造を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［２］下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［３］前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である［２］に記載の光学部材。
［４］前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である［２］に記載の光学部材。
［５］下記式（２）で表される化合物を含む硬化性組成物の硬化物を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［６］下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材形成材料。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［７］前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である［６］に記載の光学部材形成材料。
［８］前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である［６］に記載の光学部材形成材料。
［９］下記式（２）で表される化合物を含む硬化性組成物である、光学部材形成材料。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。
［１０］［６］～［８］のいずれかに記載の光学部材形成材料を製造する方法であって、
モノマー成分の少なくとも一部に前記式（１）で表される化合物を用いて前記樹脂を製造する工程を有する、光学部材形成材料の製造方法。
［１１］［９］に記載の光学部材形成材料を製造する方法であって、
前記式（２）中のＯＸが全てＯＨである化合物の前記ＯＨの少なくとも一部に、重合性官能基または反応性官能基を含む１価基を付加して前記式（２）で表される化合物を製造する工程を有する、光学部材形成材料の製造方法。
［１２］［６］～［８］のいずれかに記載の光学部材形成材料を成形する、光学部材の製造方法。
［１３］［９］に記載の光学部材形成材料を硬化する、光学部材の製造方法。 The present invention has the following aspects.
[1] An optical member including a structure represented by the following formula (i).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[2] An optical member containing a resin having a structural unit based on a compound represented by the following formula (1).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[3] The optical member according to [2], wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
[4] The optical member according to [2], wherein the resin is a polycarbonate resin or a polyester resin.
[5] An optical member containing a cured product of a curable composition containing a compound represented by the following formula (2).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[6] An optical member forming material containing a resin having a structural unit based on a compound represented by the following formula (1).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[7] The optical member forming material according to [6], wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
[8] The optical member forming material according to [6], wherein the resin is a polycarbonate resin or a polyester resin.
[9] An optical member forming material which is a curable composition containing a compound represented by the following formula (2).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
[10] A method for producing the optical member forming material according to any one of [6] to [8], comprising:
A method for producing an optical member forming material, comprising the step of producing the resin using a compound represented by the formula (1) as at least a part of the monomer components.
[11] A method for manufacturing the optical member forming material according to [9], comprising:
A monovalent group containing a polymerizable functional group or a reactive functional group is added to at least a portion of the OH of a compound in which all OX in the formula (2) are OH, and the compound is represented by the formula (2). A method for producing an optical member forming material, comprising a step of producing a compound.
[12] A method for producing an optical member, comprising molding the optical member forming material according to any one of [6] to [8].
[13] A method for producing an optical member, which comprises curing the optical member forming material according to [9].
本発明によれば、新規な骨格を持つ高屈折率の光学部材およびその製造方法、ならびに新規な骨格を持つ高屈折率の光学部材が得られる光学部材形成材料およびその製造方法を提供できる。
According to the present invention, it is possible to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same.
本発明の光学部材は、下記式（ｉ）で表される構造（以下、「構造（ｉ）」とも記す。）を含む。
The optical member of the present invention includes a structure represented by the following formula (i) (hereinafter also referred to as "structure (i)").
ここで、Ｒ１は、水素原子またはアリール基であり、
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 Here, R 1 is a hydrogen atom or an aryl group,
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different.
Ｒ１におけるアリール基としては、例えばフェニル基が挙げられる。
Ｒ１としては、高屈折率化の点からは、フェニル基が好ましく、本化合物を合成する際の反応性の容易さの点からは、水素原子が好ましい。 Examples of the aryl group for R 1 include a phenyl group.
As R 1 , a phenyl group is preferable from the viewpoint of increasing the refractive index, and a hydrogen atom is preferable from the viewpoint of ease of reactivity when synthesizing the present compound.
Ｒ１としては、高屈折率化の点からは、フェニル基が好ましく、本化合物を合成する際の反応性の容易さの点からは、水素原子が好ましい。 Examples of the aryl group for R 1 include a phenyl group.
As R 1 , a phenyl group is preferable from the viewpoint of increasing the refractive index, and a hydrogen atom is preferable from the viewpoint of ease of reactivity when synthesizing the present compound.
ａは０～５の整数であり、原料の調達のしやすさの点から、０が好ましい。
ｂは０～４の整数であり、原料の調達のしやすさの点から、０が好ましい。
Ｒ２における置換基としては、例えば炭素数１～１０のアルキル基、炭素数３～１２のシクロアルキル基、水酸基、シアノ基、アセチル基、ハロゲン原子が挙げられる。 a is an integer from 0 to 5, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
b is an integer from 0 to 4, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
Examples of the substituent for R 2 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, a cyano group, an acetyl group, and a halogen atom.
ｂは０～４の整数であり、原料の調達のしやすさの点から、０が好ましい。
Ｒ２における置換基としては、例えば炭素数１～１０のアルキル基、炭素数３～１２のシクロアルキル基、水酸基、シアノ基、アセチル基、ハロゲン原子が挙げられる。 a is an integer from 0 to 5, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
b is an integer from 0 to 4, and from the viewpoint of ease of procurement of raw materials, 0 is preferable.
Examples of the substituent for R 2 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, a cyano group, an acetyl group, and a halogen atom.
ｃおよびｄは、それぞれ独立に０～６の整数である。
好ましい一態様において、ｃおよびｄは０である。構造（ｉ）は、典型的には、後述する化合物（１）に由来する。化合物（１）において、ＨＯ－（Ｒ３Ｏ）ｃ－の末端のＯＨは、ｃが０の場合は、ＨＯ－（Ｒ３Ｏ）ｃ－が結合したベンゼン環に結合してフェノール性水酸基となり、－（ＯＲ３）ｄ－ＯＨの末端のＯＨも同様である。この場合、化合物（１）を原料にポリカーボネート樹脂やポリエステル樹脂、その他化合物とする際、反応性に優れる傾向がある。
他の好ましい一態様において、ｃおよびｄは１以上の整数である。化合物（１）において、ＨＯ－（Ｒ３Ｏ）ｃ－の末端のＯＨは、ｃが１以上の整数の場合は、Ｒ３に結合してアルコール性水酸基となり、－（ＯＲ３）ｄ－ＯＨの末端のＯＨも同様である。この場合、フェノール性水酸基の酸化により生じるキノン構造の生成が抑制され、構造（ｉ）を含む光学部材に、経時変化による黄変等の変色が発生することや、それら変色が濃くなることを抑制できる。この態様においてｃおよびｄは、耐熱性の点から、１が好ましい。 c and d are each independently an integer of 0 to 6.
In one preferred embodiment, c and d are 0. Structure (i) is typically derived from compound (1) described below. In compound (1), when c is 0, the terminal OH of HO-(R 3 O) c - becomes a phenolic hydroxyl group by bonding to the benzene ring to which HO-(R 3 O) c - is bonded. , -(OR 3 ) d The same applies to the terminal OH of -OH. In this case, when compound (1) is used as a raw material to produce polycarbonate resins, polyester resins, and other compounds, they tend to have excellent reactivity.
In another preferred embodiment, c and d are integers of 1 or more. In compound (1), when c is an integer of 1 or more, the terminal OH of HO-(R 3 O) c - bonds to R 3 to become an alcoholic hydroxyl group, and -(OR 3 ) d -OH The same applies to the terminal OH. In this case, the formation of a quinone structure caused by the oxidation of the phenolic hydroxyl group is suppressed, and the occurrence of discoloration such as yellowing due to changes over time in the optical member containing structure (i) and the deepening of such discoloration are suppressed. can. In this embodiment, c and d are preferably 1 from the viewpoint of heat resistance.
好ましい一態様において、ｃおよびｄは０である。構造（ｉ）は、典型的には、後述する化合物（１）に由来する。化合物（１）において、ＨＯ－（Ｒ３Ｏ）ｃ－の末端のＯＨは、ｃが０の場合は、ＨＯ－（Ｒ３Ｏ）ｃ－が結合したベンゼン環に結合してフェノール性水酸基となり、－（ＯＲ３）ｄ－ＯＨの末端のＯＨも同様である。この場合、化合物（１）を原料にポリカーボネート樹脂やポリエステル樹脂、その他化合物とする際、反応性に優れる傾向がある。
他の好ましい一態様において、ｃおよびｄは１以上の整数である。化合物（１）において、ＨＯ－（Ｒ３Ｏ）ｃ－の末端のＯＨは、ｃが１以上の整数の場合は、Ｒ３に結合してアルコール性水酸基となり、－（ＯＲ３）ｄ－ＯＨの末端のＯＨも同様である。この場合、フェノール性水酸基の酸化により生じるキノン構造の生成が抑制され、構造（ｉ）を含む光学部材に、経時変化による黄変等の変色が発生することや、それら変色が濃くなることを抑制できる。この態様においてｃおよびｄは、耐熱性の点から、１が好ましい。 c and d are each independently an integer of 0 to 6.
In one preferred embodiment, c and d are 0. Structure (i) is typically derived from compound (1) described below. In compound (1), when c is 0, the terminal OH of HO-(R 3 O) c - becomes a phenolic hydroxyl group by bonding to the benzene ring to which HO-(R 3 O) c - is bonded. , -(OR 3 ) d The same applies to the terminal OH of -OH. In this case, when compound (1) is used as a raw material to produce polycarbonate resins, polyester resins, and other compounds, they tend to have excellent reactivity.
In another preferred embodiment, c and d are integers of 1 or more. In compound (1), when c is an integer of 1 or more, the terminal OH of HO-(R 3 O) c - bonds to R 3 to become an alcoholic hydroxyl group, and -(OR 3 ) d -OH The same applies to the terminal OH. In this case, the formation of a quinone structure caused by the oxidation of the phenolic hydroxyl group is suppressed, and the occurrence of discoloration such as yellowing due to changes over time in the optical member containing structure (i) and the deepening of such discoloration are suppressed. can. In this embodiment, c and d are preferably 1 from the viewpoint of heat resistance.
Ｒ３におけるアルキレン基の炭素数は、例えば２～１０であり、２～４が好ましい。アルキレン基は、直鎖状でも分岐状でもよい。アルキレン基の具体例としては、エチレン基、トリメチレン基、プロピレン基、ブタン－１，２－ジイル基、ヘキシレン基が挙げられる。
The alkylene group in R 3 has, for example, 2 to 10 carbon atoms, preferably 2 to 4 carbon atoms. The alkylene group may be linear or branched. Specific examples of the alkylene group include ethylene group, trimethylene group, propylene group, butane-1,2-diyl group, and hexylene group.
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５である。
ｅおよびｆは、化合物（１）をポリカーボネート樹脂やポリエステル樹脂の原料として用いる場合には、１が特に好ましい。
化合物（１）は、そのままエポキシ樹脂の硬化剤に用いたり、化合物（１）の水酸基を重合性官能基や反応性官能基を含む基に置換し、硬化性組成物に含有させて用いたりすることもできる。このような場合には、ｅおよびｆは、硬化性組成物を硬化させた際に架橋密度が高くなることにより、その硬化物の機械強度や耐熱性が高まることから、それぞれ独立に１～４の整数であることが好ましい。
ｇおよびｈは、原料調達のしやすさの点から、それぞれ独立に１～２の整数が好ましく、１が特に好ましい。
Ｒ４における置換基としては、例えば炭素数１～１０のアルキル基、炭素数３～１２のシクロアルキル基、水酸基、アセチル基、ハロゲン原子、－（ＯＲ３）ｋＯＨが挙げられる。Ｒ３は前記と同様である。ｋは０～６の整数である。
Ｒ４としては、原料調達のしやすさの点から、アルキル基が好ましい。アルキル基の炭素数は、例えば１～１０であり、１～２が好ましい。アルキル基は、直鎖状でも分岐状でもよい。 e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. be.
e and f are particularly preferably 1 when the compound (1) is used as a raw material for polycarbonate resin or polyester resin.
Compound (1) can be used as it is as a curing agent for epoxy resins, or the hydroxyl group of compound (1) can be replaced with a group containing a polymerizable functional group or a reactive functional group, and it can be incorporated into a curable composition. You can also do that. In such a case, e and f each independently range from 1 to 4, since the crosslinking density increases when the curable composition is cured, thereby increasing the mechanical strength and heat resistance of the cured product. is preferably an integer of .
From the viewpoint of ease of raw material procurement, g and h are each independently preferably an integer of 1 to 2, and 1 is particularly preferred.
Examples of the substituent for R 4 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, an acetyl group, a halogen atom, and -(OR 3 ) k OH. R3 is the same as above. k is an integer from 0 to 6.
R 4 is preferably an alkyl group from the viewpoint of ease of raw material procurement. The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 2. The alkyl group may be linear or branched.
ｅおよびｆは、化合物（１）をポリカーボネート樹脂やポリエステル樹脂の原料として用いる場合には、１が特に好ましい。
化合物（１）は、そのままエポキシ樹脂の硬化剤に用いたり、化合物（１）の水酸基を重合性官能基や反応性官能基を含む基に置換し、硬化性組成物に含有させて用いたりすることもできる。このような場合には、ｅおよびｆは、硬化性組成物を硬化させた際に架橋密度が高くなることにより、その硬化物の機械強度や耐熱性が高まることから、それぞれ独立に１～４の整数であることが好ましい。
ｇおよびｈは、原料調達のしやすさの点から、それぞれ独立に１～２の整数が好ましく、１が特に好ましい。
Ｒ４における置換基としては、例えば炭素数１～１０のアルキル基、炭素数３～１２のシクロアルキル基、水酸基、アセチル基、ハロゲン原子、－（ＯＲ３）ｋＯＨが挙げられる。Ｒ３は前記と同様である。ｋは０～６の整数である。
Ｒ４としては、原料調達のしやすさの点から、アルキル基が好ましい。アルキル基の炭素数は、例えば１～１０であり、１～２が好ましい。アルキル基は、直鎖状でも分岐状でもよい。 e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. be.
e and f are particularly preferably 1 when the compound (1) is used as a raw material for polycarbonate resin or polyester resin.
Compound (1) can be used as it is as a curing agent for epoxy resins, or the hydroxyl group of compound (1) can be replaced with a group containing a polymerizable functional group or a reactive functional group, and it can be incorporated into a curable composition. You can also do that. In such a case, e and f each independently range from 1 to 4, since the crosslinking density increases when the curable composition is cured, thereby increasing the mechanical strength and heat resistance of the cured product. is preferably an integer of .
From the viewpoint of ease of raw material procurement, g and h are each independently preferably an integer of 1 to 2, and 1 is particularly preferred.
Examples of the substituent for R 4 include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a hydroxyl group, an acetyl group, a halogen atom, and -(OR 3 ) k OH. R3 is the same as above. k is an integer from 0 to 6.
R 4 is preferably an alkyl group from the viewpoint of ease of raw material procurement. The number of carbon atoms in the alkyl group is, for example, 1 to 10, preferably 1 to 2. The alkyl group may be linear or branched.
化合物（１）をモノマー成分の少なくとも一部に用いてポリカーボネート樹脂またはポリエステル樹脂を製造する場合には、ｅおよびｆが１であり、ｇおよびｈがそれぞれ独立に１～２の整数であり、Ｒ４がアルキル基であることが好ましい。このときのＲ１、ａ、ｂ、ｃ、ｄ、Ｒ３それぞれの好ましい態様は前記と同様である。
化合物（１）の水酸基に重合性官能基または反応性官能基を含む１価基を付加し、硬化性組成物に含有させる場合には、ｅおよびｆがそれぞれ独立に１～４の整数であり、ｇおよびｈがそれぞれ独立に１～２の整数であり、Ｒ４がアルキル基であることが好ましい。この場合、ｅおよびｆの値が大きいほど、硬化性組成物を硬化させた際に架橋密度が高くなることにより、その硬化物の機械強度や耐熱性が高まる傾向がある。このときのＲ１、ａ、ｂ、ｃ、ｄ、Ｒ３それぞれの好ましい態様は前記と同様である。 When producing a polycarbonate resin or a polyester resin using compound (1) as at least a part of the monomer component, e and f are 1, g and h are each independently an integer of 1 to 2, and R It is preferred that 4 is an alkyl group. At this time, preferred embodiments of each of R 1 , a, b, c, d, and R 3 are the same as described above.
When adding a monovalent group containing a polymerizable functional group or a reactive functional group to the hydroxyl group of compound (1) and incorporating it into the curable composition, e and f are each independently an integer of 1 to 4; , g and h are each independently an integer of 1 to 2, and R 4 is preferably an alkyl group. In this case, the larger the values of e and f, the higher the crosslinking density when the curable composition is cured, which tends to increase the mechanical strength and heat resistance of the cured product. At this time, preferred embodiments of each of R 1 , a, b, c, d, and R 3 are the same as described above.
化合物（１）の水酸基に重合性官能基または反応性官能基を含む１価基を付加し、硬化性組成物に含有させる場合には、ｅおよびｆがそれぞれ独立に１～４の整数であり、ｇおよびｈがそれぞれ独立に１～２の整数であり、Ｒ４がアルキル基であることが好ましい。この場合、ｅおよびｆの値が大きいほど、硬化性組成物を硬化させた際に架橋密度が高くなることにより、その硬化物の機械強度や耐熱性が高まる傾向がある。このときのＲ１、ａ、ｂ、ｃ、ｄ、Ｒ３それぞれの好ましい態様は前記と同様である。 When producing a polycarbonate resin or a polyester resin using compound (1) as at least a part of the monomer component, e and f are 1, g and h are each independently an integer of 1 to 2, and R It is preferred that 4 is an alkyl group. At this time, preferred embodiments of each of R 1 , a, b, c, d, and R 3 are the same as described above.
When adding a monovalent group containing a polymerizable functional group or a reactive functional group to the hydroxyl group of compound (1) and incorporating it into the curable composition, e and f are each independently an integer of 1 to 4; , g and h are each independently an integer of 1 to 2, and R 4 is preferably an alkyl group. In this case, the larger the values of e and f, the higher the crosslinking density when the curable composition is cured, which tends to increase the mechanical strength and heat resistance of the cured product. At this time, preferred embodiments of each of R 1 , a, b, c, d, and R 3 are the same as described above.
〔光学部材（１）〕
本発明の光学部材の一態様として、下記式（１）で表される化合物（以下、「化合物（１）」とも記す。）に基づく構成単位を有する樹脂（以下、「樹脂Ａ」とも記す。）を含む光学部材（以下、「光学部材（１）」とも記す。）が挙げられる。
化合物（１）に基づく構成単位は、前記した構造（ｉ）を含む。 [Optical member (1)]
One embodiment of the optical member of the present invention is a resin (hereinafter also referred to as "resin A") having a structural unit based on a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"). ) (hereinafter also referred to as "optical member (1)").
The structural unit based on compound (1) includes the structure (i) described above.
本発明の光学部材の一態様として、下記式（１）で表される化合物（以下、「化合物（１）」とも記す。）に基づく構成単位を有する樹脂（以下、「樹脂Ａ」とも記す。）を含む光学部材（以下、「光学部材（１）」とも記す。）が挙げられる。
化合物（１）に基づく構成単位は、前記した構造（ｉ）を含む。 [Optical member (1)]
One embodiment of the optical member of the present invention is a resin (hereinafter also referred to as "resin A") having a structural unit based on a compound represented by the following formula (1) (hereinafter also referred to as "compound (1)"). ) (hereinafter also referred to as "optical member (1)").
The structural unit based on compound (1) includes the structure (i) described above.
式（１）中、Ｒ１、ａ、ｂ、Ｒ２、ｃ、ｄ、Ｒ３、ｅ、ｆ、ｇ、ｈおよびＲ４はそれぞれ前記したとおりである。
In formula (1), R 1 , a, b, R 2 , c, d, R 3 , e, f, g, h and R 4 are each as described above.
樹脂Ａとしては、例えば、多価ヒドロキシ化合物をモノマー成分とする樹脂であって、多価ヒドロキシ化合物の少なくとも一部が化合物（１）である樹脂が挙げられる。
多価ヒドロキシ化合物は、２以上の水酸基を有する化合物である。 Examples of the resin A include resins containing a polyvalent hydroxy compound as a monomer component, in which at least a portion of the polyvalent hydroxy compound is compound (1).
A polyhydric hydroxy compound is a compound having two or more hydroxyl groups.
多価ヒドロキシ化合物は、２以上の水酸基を有する化合物である。 Examples of the resin A include resins containing a polyvalent hydroxy compound as a monomer component, in which at least a portion of the polyvalent hydroxy compound is compound (1).
A polyhydric hydroxy compound is a compound having two or more hydroxyl groups.
多価ヒドロキシ化合物をモノマー成分とする樹脂の一例として、ポリカーボネート樹脂が挙げられる。
モノマー成分として化合物（１）を用いたポリカーボネート樹脂としては、例えば、下記式（ａ１）で表される構成単位（以下、「構成単位（ａ１）」とも記す。）を有するポリカーボネート樹脂が挙げられる。 An example of a resin containing a polyhydric hydroxy compound as a monomer component is a polycarbonate resin.
Examples of polycarbonate resins using compound (1) as a monomer component include polycarbonate resins having a structural unit represented by the following formula (a1) (hereinafter also referred to as "constituent unit (a1)").
モノマー成分として化合物（１）を用いたポリカーボネート樹脂としては、例えば、下記式（ａ１）で表される構成単位（以下、「構成単位（ａ１）」とも記す。）を有するポリカーボネート樹脂が挙げられる。 An example of a resin containing a polyhydric hydroxy compound as a monomer component is a polycarbonate resin.
Examples of polycarbonate resins using compound (1) as a monomer component include polycarbonate resins having a structural unit represented by the following formula (a1) (hereinafter also referred to as "constituent unit (a1)").
ポリカーボネート樹脂が有する構成単位（ａ１）は１種でもよく２種以上でもよい。
ポリカーボネート樹脂は、構成単位（ａ１）以外の他の構成単位をさらに有していてもよい。
他の構成単位としては、例えば、化合物（１）以外の他の多価ヒドロキシ化合物に基づく構成単位（以下、「構成単位（ａ２）」とも記す。）が挙げられる。
構成単位（ａ２）は、下記式（ａ２）で表される。 The polycarbonate resin may have one or more types of structural units (a1).
The polycarbonate resin may further have other structural units other than the structural unit (a1).
Examples of other structural units include structural units based on polyvalent hydroxy compounds other than compound (1) (hereinafter also referred to as "structural units (a2)").
The structural unit (a2) is represented by the following formula (a2).
ポリカーボネート樹脂は、構成単位（ａ１）以外の他の構成単位をさらに有していてもよい。
他の構成単位としては、例えば、化合物（１）以外の他の多価ヒドロキシ化合物に基づく構成単位（以下、「構成単位（ａ２）」とも記す。）が挙げられる。
構成単位（ａ２）は、下記式（ａ２）で表される。 The polycarbonate resin may have one or more types of structural units (a1).
The polycarbonate resin may further have other structural units other than the structural unit (a1).
Examples of other structural units include structural units based on polyvalent hydroxy compounds other than compound (1) (hereinafter also referred to as "structural units (a2)").
The structural unit (a2) is represented by the following formula (a2).
Ｒ６は、他の多価ヒドロキシ化合物から２個の水酸基を除いた残基である。他の多価ヒドロキシ化合物は、典型的には、ジヒドロキシ化合物である。
他の多価ヒドロキシ化合物としては、特に制限はなく、ポリカーボネート樹脂のモノマー成分として公知のものを用いることができる。他の多価ヒドロキシ化合物としては、例えば芳香族ジヒドロキシ化合物等の芳香族多価ヒドロキシ化合物、脂肪族ジヒドロキシ化合物等の脂肪族多価ヒドロキシ化合物が挙げられる。芳香族ジヒドロキシ化合物としては、例えばヒドロキノン、レゾルシン等のフェノール化合物、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＢ、ビスフェノールＡＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＳ、ビスフェノールＺ、ビスフェノールＣＤＥ、ビスフェノールフルオレン等のビスフェノール化合物、ビスナフトールフルオレン、４，４’－ジヒドロキシビフェニル等が挙げられる。脂肪族ジヒドロキシ化合物としては、例えばエチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，４－シクロヘキサンジメタノール等が挙げられる。
ポリカーボネート樹脂が有する構成単位（ａ２）は１種でもよく２種以上でもよい。 R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound. Other polyhydric hydroxy compounds are typically dihydroxy compounds.
There are no particular limitations on the other polyhydric hydroxy compounds, and those known as monomer components of polycarbonate resins can be used. Examples of other polyhydric hydroxy compounds include aromatic polyhydroxy compounds such as aromatic dihydroxy compounds, and aliphatic polyhydroxy compounds such as aliphatic dihydroxy compounds. Examples of aromatic dihydroxy compounds include phenolic compounds such as hydroquinone and resorcinol; bisphenol compounds such as bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol C, bisphenol E, bisphenol S, bisphenol Z, bisphenol CDE, and bisphenol fluorene; Examples include bisnaphtholfluorene and 4,4'-dihydroxybiphenyl. Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.
The polycarbonate resin may have one or more structural units (a2).
他の多価ヒドロキシ化合物としては、特に制限はなく、ポリカーボネート樹脂のモノマー成分として公知のものを用いることができる。他の多価ヒドロキシ化合物としては、例えば芳香族ジヒドロキシ化合物等の芳香族多価ヒドロキシ化合物、脂肪族ジヒドロキシ化合物等の脂肪族多価ヒドロキシ化合物が挙げられる。芳香族ジヒドロキシ化合物としては、例えばヒドロキノン、レゾルシン等のフェノール化合物、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＢ、ビスフェノールＡＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＳ、ビスフェノールＺ、ビスフェノールＣＤＥ、ビスフェノールフルオレン等のビスフェノール化合物、ビスナフトールフルオレン、４，４’－ジヒドロキシビフェニル等が挙げられる。脂肪族ジヒドロキシ化合物としては、例えばエチレングリコール、１，３－プロパンジオール、１，４－ブタンジオール、１，４－シクロヘキサンジメタノール等が挙げられる。
ポリカーボネート樹脂が有する構成単位（ａ２）は１種でもよく２種以上でもよい。 R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound. Other polyhydric hydroxy compounds are typically dihydroxy compounds.
There are no particular limitations on the other polyhydric hydroxy compounds, and those known as monomer components of polycarbonate resins can be used. Examples of other polyhydric hydroxy compounds include aromatic polyhydroxy compounds such as aromatic dihydroxy compounds, and aliphatic polyhydroxy compounds such as aliphatic dihydroxy compounds. Examples of aromatic dihydroxy compounds include phenolic compounds such as hydroquinone and resorcinol; bisphenol compounds such as bisphenol A, bisphenol F, bisphenol B, bisphenol AP, bisphenol C, bisphenol E, bisphenol S, bisphenol Z, bisphenol CDE, and bisphenol fluorene; Examples include bisnaphtholfluorene and 4,4'-dihydroxybiphenyl. Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol.
The polycarbonate resin may have one or more structural units (a2).
多価ヒドロキシ化合物をモノマー成分とする樹脂の他の一例として、ポリエステル樹脂が挙げられる。
モノマー成分として化合物（１）を用いたポリエステル樹脂としては、例えば、下記式（ｂ１）で表される構成単位（以下、「構成単位（ｂ１）」とも記す。）を有するポリエステル樹脂が挙げられる。 Another example of a resin containing a polyhydric hydroxy compound as a monomer component is a polyester resin.
Examples of polyester resins using compound (1) as a monomer component include polyester resins having a structural unit represented by the following formula (b1) (hereinafter also referred to as "constituent unit (b1)").
モノマー成分として化合物（１）を用いたポリエステル樹脂としては、例えば、下記式（ｂ１）で表される構成単位（以下、「構成単位（ｂ１）」とも記す。）を有するポリエステル樹脂が挙げられる。 Another example of a resin containing a polyhydric hydroxy compound as a monomer component is a polyester resin.
Examples of polyester resins using compound (1) as a monomer component include polyester resins having a structural unit represented by the following formula (b1) (hereinafter also referred to as "constituent unit (b1)").
Ｒ５は、ジカルボン酸から２個のカルボキシ基を除いた残基である。
ジカルボン酸としては、特に制限はなく、ポリエステル樹脂のモノマー成分として公知のものを用いることができる。ジカルボン酸の例としては、テレフタル酸、２，６－ナフタレンジカルボン酸が挙げられる。 R 5 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
The dicarboxylic acid is not particularly limited, and those known as monomer components of polyester resins can be used. Examples of dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid.
ジカルボン酸としては、特に制限はなく、ポリエステル樹脂のモノマー成分として公知のものを用いることができる。ジカルボン酸の例としては、テレフタル酸、２，６－ナフタレンジカルボン酸が挙げられる。 R 5 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
The dicarboxylic acid is not particularly limited, and those known as monomer components of polyester resins can be used. Examples of dicarboxylic acids include terephthalic acid and 2,6-naphthalene dicarboxylic acid.
ポリエステル樹脂が有する構成単位（ｂ１）は１種でもよく２種以上でもよい。
ポリエステル樹脂は、構成単位（ｂ１）以外の他の構成単位をさらに有していてもよい。
他の構成単位としては、例えば、下記式（ｂ２）で表される構成単位（以下、「構成単位（ｂ２）」とも記す。）が挙げられる。 The polyester resin may have one or more types of structural units (b1).
The polyester resin may further have other structural units other than the structural unit (b1).
Examples of other structural units include a structural unit represented by the following formula (b2) (hereinafter also referred to as "structural unit (b2)").
ポリエステル樹脂は、構成単位（ｂ１）以外の他の構成単位をさらに有していてもよい。
他の構成単位としては、例えば、下記式（ｂ２）で表される構成単位（以下、「構成単位（ｂ２）」とも記す。）が挙げられる。 The polyester resin may have one or more types of structural units (b1).
The polyester resin may further have other structural units other than the structural unit (b1).
Examples of other structural units include a structural unit represented by the following formula (b2) (hereinafter also referred to as "structural unit (b2)").
Ｒ６は、他の多価ヒドロキシ化合物から２個の水酸基を除いた残基であり、Ｒ７は、ジカルボン酸から２個のカルボキシ基を除いた残基である。
他の多価ヒドロキシ化合物、ジカルボン酸はそれぞれ前記と同様のものが挙げられる。
ポリエステル樹脂が有する構成単位（ｂ２）は１種でもよく２種以上でもよい。 R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound, and R 7 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
Examples of other polyhydric hydroxy compounds and dicarboxylic acids include those mentioned above.
The polyester resin may have one or more types of structural units (b2).
他の多価ヒドロキシ化合物、ジカルボン酸はそれぞれ前記と同様のものが挙げられる。
ポリエステル樹脂が有する構成単位（ｂ２）は１種でもよく２種以上でもよい。 R 6 is a residue obtained by removing two hydroxyl groups from another polyhydric hydroxy compound, and R 7 is a residue obtained by removing two carboxyl groups from a dicarboxylic acid.
Examples of other polyhydric hydroxy compounds and dicarboxylic acids include those mentioned above.
The polyester resin may have one or more types of structural units (b2).
光学部材（１）は、必要に応じて、本発明の効果を損なわない範囲で、樹脂Ａ以外の他の成分をさらに含んでいてもよい。他の成分としては、例えば、着色剤、無機充填剤、有機充填剤、酸化防止剤、その他の各種の添加剤が挙げられる。他の成分は１種を単独で用いてもよく２種以上を併用してもよい。
The optical member (1) may further contain other components other than resin A, if necessary, within a range that does not impair the effects of the present invention. Examples of other components include colorants, inorganic fillers, organic fillers, antioxidants, and other various additives. As for the other components, one kind may be used alone or two or more kinds may be used in combination.
＜光学部材（１）の製造方法＞
光学部材（１）は、例えば、樹脂Ａを含む光学部材形成材料（以下、「光学部材形成材料（１）」とも記す。）を成形することにより製造できる。
光学部材形成材料（１）は、必要に応じて、本発明の効果を損なわない範囲で、樹脂Ａ以外の他の成分をさらに含んでいてもよい。他の成分としては、前記と同様のものが挙げられる。光学部材形成材料（１）の製造方法については後で詳しく説明する。 <Method for manufacturing optical member (1)>
The optical member (1) can be manufactured, for example, by molding an optical member forming material containing resin A (hereinafter also referred to as "optical member forming material (1)").
The optical member forming material (1) may further contain other components than the resin A, if necessary, within a range that does not impair the effects of the present invention. Other components include those mentioned above. The method for manufacturing the optical member forming material (1) will be explained in detail later.
光学部材（１）は、例えば、樹脂Ａを含む光学部材形成材料（以下、「光学部材形成材料（１）」とも記す。）を成形することにより製造できる。
光学部材形成材料（１）は、必要に応じて、本発明の効果を損なわない範囲で、樹脂Ａ以外の他の成分をさらに含んでいてもよい。他の成分としては、前記と同様のものが挙げられる。光学部材形成材料（１）の製造方法については後で詳しく説明する。 <Method for manufacturing optical member (1)>
The optical member (1) can be manufactured, for example, by molding an optical member forming material containing resin A (hereinafter also referred to as "optical member forming material (1)").
The optical member forming material (1) may further contain other components than the resin A, if necessary, within a range that does not impair the effects of the present invention. Other components include those mentioned above. The method for manufacturing the optical member forming material (1) will be explained in detail later.
光学部材形成材料（１）の成形方法としては、熱可塑性樹脂の成形方法として公知の方法を用いることができ、例えば、射出成形、トランスファー成形、押出成形、ブロー成形、真空成形、圧縮成形等が挙げられる。
As a molding method for the optical member forming material (1), known methods for molding thermoplastic resins can be used, such as injection molding, transfer molding, extrusion molding, blow molding, vacuum molding, compression molding, etc. Can be mentioned.
＜光学部材形成材料（１）の製造方法＞
光学部材形成材料（１）は、例えば、モノマー成分の少なくとも一部に化合物（１）を用いて樹脂Ａを製造し、必要に応じて他の成分を混合することにより製造できる。
樹脂Ａは、モノマー成分の少なくとも一部に化合物（１）を用いる以外は、公知の製造方法により製造できる。 <Method for manufacturing optical member forming material (1)>
Optical member forming material (1) can be produced, for example, by producing resin A using compound (1) as at least part of the monomer components, and mixing other components as necessary.
Resin A can be manufactured by a known manufacturing method except for using compound (1) as at least a part of the monomer components.
光学部材形成材料（１）は、例えば、モノマー成分の少なくとも一部に化合物（１）を用いて樹脂Ａを製造し、必要に応じて他の成分を混合することにより製造できる。
樹脂Ａは、モノマー成分の少なくとも一部に化合物（１）を用いる以外は、公知の製造方法により製造できる。 <Method for manufacturing optical member forming material (1)>
Optical member forming material (1) can be produced, for example, by producing resin A using compound (1) as at least part of the monomer components, and mixing other components as necessary.
Resin A can be manufactured by a known manufacturing method except for using compound (1) as at least a part of the monomer components.
樹脂Ａを製造する前に、化合物（１）を製造してもよい。
化合物（１）は、例えば、以下の工程Ａを有する製造方法により製造できる。
工程Ａ：下記式（１ａ）で表されるビフェニル化合物と、下記式（１ｂ）で表されるヒドロキシ化合物と、下記式（１ｃ）で表されるヒドロキシ化合物とを反応させて下記式（１－１）で表される化合物（以下、「化合物（１－１）」とも記す。）を得る工程。
必要に応じて、工程Ａの後、下記工程Ｂを行う。
工程Ｂ：工程Ａで得られた化合物（１－１）の水酸基に１以上のオキシアルキレン基を付加する工程。 Before producing resin A, compound (1) may be produced.
Compound (1) can be produced, for example, by a production method including Step A below.
Step A: A biphenyl compound represented by the following formula (1a), a hydroxy compound represented by the following formula (1b), and a hydroxy compound represented by the following formula (1c) are reacted to form the following formula (1- A step of obtaining the compound represented by 1) (hereinafter also referred to as "compound (1-1)").
If necessary, after step A, the following step B is performed.
Step B: A step of adding one or more oxyalkylene groups to the hydroxyl group of compound (1-1) obtained in Step A.
化合物（１）は、例えば、以下の工程Ａを有する製造方法により製造できる。
工程Ａ：下記式（１ａ）で表されるビフェニル化合物と、下記式（１ｂ）で表されるヒドロキシ化合物と、下記式（１ｃ）で表されるヒドロキシ化合物とを反応させて下記式（１－１）で表される化合物（以下、「化合物（１－１）」とも記す。）を得る工程。
必要に応じて、工程Ａの後、下記工程Ｂを行う。
工程Ｂ：工程Ａで得られた化合物（１－１）の水酸基に１以上のオキシアルキレン基を付加する工程。 Before producing resin A, compound (1) may be produced.
Compound (1) can be produced, for example, by a production method including Step A below.
Step A: A biphenyl compound represented by the following formula (1a), a hydroxy compound represented by the following formula (1b), and a hydroxy compound represented by the following formula (1c) are reacted to form the following formula (1- A step of obtaining the compound represented by 1) (hereinafter also referred to as "compound (1-1)").
If necessary, after step A, the following step B is performed.
Step B: A step of adding one or more oxyalkylene groups to the hydroxyl group of compound (1-1) obtained in Step A.
（ビフェニル化合物）
式（１ａ）中、Ｒ１、ａ、ｂ、Ｒ２はそれぞれ前記したとおりである。
ビフェニル化合物としては、例えば、４－ビフェニルアルデヒド、４－ブロモ－４’－ビフェニルアルデヒド、４－ベンゾイルビフェニル、４－ブロモ－４’－ベンゾイルビフェニルが挙げられる。これらのビフェニル化合物は１種を単独で用いてもよく２種以上を併用してもよい。これらの中でも、原料の調達のしやすさの点では、４－ビフェニルアルデヒドが好ましい。臭素原子を有することで、生成する化合物（１）がより高屈折率を発現できる点では、４－ブロモ－４’－ビフェニルアルデヒドが好ましい。 (Biphenyl compound)
In formula (1a), R 1 , a, b, and R 2 are each as described above.
Examples of the biphenyl compound include 4-biphenylaldehyde, 4-bromo-4'-biphenylaldehyde, 4-benzoylbiphenyl, and 4-bromo-4'-benzoylbiphenyl. These biphenyl compounds may be used alone or in combination of two or more. Among these, 4-biphenylaldehyde is preferred in terms of ease of procurement of raw materials. 4-Bromo-4'-biphenylaldehyde is preferred because the compound (1) produced can exhibit a higher refractive index by having a bromine atom.
式（１ａ）中、Ｒ１、ａ、ｂ、Ｒ２はそれぞれ前記したとおりである。
ビフェニル化合物としては、例えば、４－ビフェニルアルデヒド、４－ブロモ－４’－ビフェニルアルデヒド、４－ベンゾイルビフェニル、４－ブロモ－４’－ベンゾイルビフェニルが挙げられる。これらのビフェニル化合物は１種を単独で用いてもよく２種以上を併用してもよい。これらの中でも、原料の調達のしやすさの点では、４－ビフェニルアルデヒドが好ましい。臭素原子を有することで、生成する化合物（１）がより高屈折率を発現できる点では、４－ブロモ－４’－ビフェニルアルデヒドが好ましい。 (Biphenyl compound)
In formula (1a), R 1 , a, b, and R 2 are each as described above.
Examples of the biphenyl compound include 4-biphenylaldehyde, 4-bromo-4'-biphenylaldehyde, 4-benzoylbiphenyl, and 4-bromo-4'-benzoylbiphenyl. These biphenyl compounds may be used alone or in combination of two or more. Among these, 4-biphenylaldehyde is preferred in terms of ease of procurement of raw materials. 4-Bromo-4'-biphenylaldehyde is preferred because the compound (1) produced can exhibit a higher refractive index by having a bromine atom.
（ヒドロキシ化合物）
式（１ｂ）、（１ｃ）中、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、Ｒ３およびＲ４はそれぞれ前記したとおりである。
式（１ｂ）で表されるヒドロキシ化合物と式（１ｃ）で表されるヒドロキシ化合物は同じものであっても異なるものであってもよい。以下、式（１ｂ）で表されるヒドロキシ化合物と式（１ｃ）で表されるヒドロキシ化合物を総称して単に「ヒドロキシ化合物」とも記す。
ヒドロキシ化合物としては、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－フェニルフェノール、ｐ－クルミフェノール、ｐ－ノニルフェノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＢ、ビスフェノールＡＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＳ、ビスフェノールＺ、ビスフェノールＣＤＥ、ジヒドロキシジフェニルメタン、スチレン化フェノール、炭素数２～９のアルキル基で置換されたアルキルフェノール、精製カシューナッツシェルリキッドの主成分である側鎖不飽和結合を有する長鎖アルキルで置換されたアルキルフェノール、キシレノール、カテコール、レゾルシン、ヒドロキノン、ピロガロール等公知のフェノール誘導体、更に塩素または臭素で置換されたハロゲン化フェノール等が挙げられる。これらのヒドロキシ化合物は１種を単独で用いてもよく２種以上を併用してもよい。これら中でも、原料の調達のしやすさの点から、フェノール、クレゾール、レゾルシンが好ましい。 (Hydroxy compound)
In formulas (1b) and (1c), c, d, e, f, g, h, R 3 and R 4 are each as described above.
The hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) may be the same or different. Hereinafter, the hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) will be collectively referred to as simply "hydroxy compound."
Hydroxy compounds include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-phenylphenol, p-walnutphenol, p-nonylphenol, bisphenol A, bisphenol F, bisphenol B, and bisphenol AP. , bisphenol C, bisphenol E, bisphenol S, bisphenol Z, bisphenol CDE, dihydroxydiphenylmethane, styrenated phenol, alkylphenol substituted with an alkyl group having 2 to 9 carbon atoms, unsaturated side chain that is the main component of purified cashew nut shell liquid Known phenol derivatives such as alkylphenols substituted with a long-chain alkyl having a bond, xylenol, catechol, resorcinol, hydroquinone, and pyrogallol, and halogenated phenols substituted with chlorine or bromine may be mentioned. These hydroxy compounds may be used alone or in combination of two or more. Among these, phenol, cresol, and resorcinol are preferred from the viewpoint of easy procurement of raw materials.
式（１ｂ）、（１ｃ）中、ｃ、ｄ、ｅ、ｆ、ｇ、ｈ、Ｒ３およびＲ４はそれぞれ前記したとおりである。
式（１ｂ）で表されるヒドロキシ化合物と式（１ｃ）で表されるヒドロキシ化合物は同じものであっても異なるものであってもよい。以下、式（１ｂ）で表されるヒドロキシ化合物と式（１ｃ）で表されるヒドロキシ化合物を総称して単に「ヒドロキシ化合物」とも記す。
ヒドロキシ化合物としては、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－フェニルフェノール、ｐ－クルミフェノール、ｐ－ノニルフェノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＢ、ビスフェノールＡＰ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＳ、ビスフェノールＺ、ビスフェノールＣＤＥ、ジヒドロキシジフェニルメタン、スチレン化フェノール、炭素数２～９のアルキル基で置換されたアルキルフェノール、精製カシューナッツシェルリキッドの主成分である側鎖不飽和結合を有する長鎖アルキルで置換されたアルキルフェノール、キシレノール、カテコール、レゾルシン、ヒドロキノン、ピロガロール等公知のフェノール誘導体、更に塩素または臭素で置換されたハロゲン化フェノール等が挙げられる。これらのヒドロキシ化合物は１種を単独で用いてもよく２種以上を併用してもよい。これら中でも、原料の調達のしやすさの点から、フェノール、クレゾール、レゾルシンが好ましい。 (Hydroxy compound)
In formulas (1b) and (1c), c, d, e, f, g, h, R 3 and R 4 are each as described above.
The hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) may be the same or different. Hereinafter, the hydroxy compound represented by formula (1b) and the hydroxy compound represented by formula (1c) will be collectively referred to as simply "hydroxy compound."
Hydroxy compounds include phenol, o-cresol, m-cresol, p-cresol, p-tert-butylphenol, p-phenylphenol, p-walnutphenol, p-nonylphenol, bisphenol A, bisphenol F, bisphenol B, and bisphenol AP. , bisphenol C, bisphenol E, bisphenol S, bisphenol Z, bisphenol CDE, dihydroxydiphenylmethane, styrenated phenol, alkylphenol substituted with an alkyl group having 2 to 9 carbon atoms, unsaturated side chain that is the main component of purified cashew nut shell liquid Known phenol derivatives such as alkylphenols substituted with a long-chain alkyl having a bond, xylenol, catechol, resorcinol, hydroquinone, and pyrogallol, and halogenated phenols substituted with chlorine or bromine may be mentioned. These hydroxy compounds may be used alone or in combination of two or more. Among these, phenol, cresol, and resorcinol are preferred from the viewpoint of easy procurement of raw materials.
（工程Ａ）
ビフェニル化合物とヒドロキシ化合物とを反応させる際のビフェニル化合物とヒドロキシ化合物とのモル比（ビフェニル化合物／ヒドロキシ化合物）は、０．０１～１．００が好ましく、０．０５～０．５０がより好ましい。
ビフェニル化合物／ヒドロキシ化合物のモル比が１．００以下であれば、１分子のビフェニル化合物に２分子のヒドロキシ化合物が付加した化合物（１－１）が主成分として生成される傾向がある。
ビフェニル化合物／ヒドロキシ化合物のモル比が１．００を超えると、ビフェニル化合物とヒドロキシ化合物が交互に付加しやすくなり、結果として化合物（１－１）の収率が低くなるおそれがある。 (Process A)
The molar ratio between the biphenyl compound and the hydroxy compound (biphenyl compound/hydroxy compound) when the biphenyl compound and the hydroxy compound are reacted is preferably 0.01 to 1.00, more preferably 0.05 to 0.50.
If the molar ratio of biphenyl compound/hydroxy compound is 1.00 or less, a compound (1-1) in which two molecules of hydroxy compound are added to one molecule of biphenyl compound tends to be produced as a main component.
When the biphenyl compound/hydroxy compound molar ratio exceeds 1.00, the biphenyl compound and the hydroxy compound tend to be added alternately, which may result in a low yield of compound (1-1).
ビフェニル化合物とヒドロキシ化合物とを反応させる際のビフェニル化合物とヒドロキシ化合物とのモル比（ビフェニル化合物／ヒドロキシ化合物）は、０．０１～１．００が好ましく、０．０５～０．５０がより好ましい。
ビフェニル化合物／ヒドロキシ化合物のモル比が１．００以下であれば、１分子のビフェニル化合物に２分子のヒドロキシ化合物が付加した化合物（１－１）が主成分として生成される傾向がある。
ビフェニル化合物／ヒドロキシ化合物のモル比が１．００を超えると、ビフェニル化合物とヒドロキシ化合物が交互に付加しやすくなり、結果として化合物（１－１）の収率が低くなるおそれがある。 (Process A)
The molar ratio between the biphenyl compound and the hydroxy compound (biphenyl compound/hydroxy compound) when the biphenyl compound and the hydroxy compound are reacted is preferably 0.01 to 1.00, more preferably 0.05 to 0.50.
If the molar ratio of biphenyl compound/hydroxy compound is 1.00 or less, a compound (1-1) in which two molecules of hydroxy compound are added to one molecule of biphenyl compound tends to be produced as a main component.
When the biphenyl compound/hydroxy compound molar ratio exceeds 1.00, the biphenyl compound and the hydroxy compound tend to be added alternately, which may result in a low yield of compound (1-1).
典型的には、酸触媒の存在下でビフェニル化合物とヒドロキシ化合物とを反応させる。酸触媒を用いることで、ビフェニル化合物とヒドロキシ化合物との反応が容易に進行する。
酸触媒としては、例えば塩酸、硫酸、リン酸等の無機酸；シュウ酸、酢酸、クエン酸、酒石酸、安息香酸、パラトルエンスルホン酸等の有機酸；酢酸亜鉛、ホウ酸亜鉛等の有機酸塩；スルホン基やカルボン酸基を有するイオン交換樹脂等が挙げられる。これらの中でも、副反応による副生物の生成が抑制されると同時に、反応終了後、水洗処理などにより、容易に脱触媒を行うことができる点で、シュウ酸、塩酸、硫酸、パラトルエンスルホン酸が好ましい。これらの酸触媒は１種を単独で用いてもよく２種以上を併用してもよい。
酸触媒の使用量は、例えば、ビフェニル化合物１００質量部に対して０．０１～１００質量部である。 Typically, a biphenyl compound and a hydroxy compound are reacted in the presence of an acid catalyst. By using an acid catalyst, the reaction between the biphenyl compound and the hydroxy compound proceeds easily.
Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, acetic acid, citric acid, tartaric acid, benzoic acid, and paratoluenesulfonic acid; and organic acid salts such as zinc acetate and zinc borate. ; Examples include ion exchange resins having sulfone groups and carboxylic acid groups. Among these, oxalic acid, hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid are useful because they suppress the generation of byproducts due to side reactions and at the same time, they can be easily decatalyzed by washing with water after the reaction. is preferred. These acid catalysts may be used alone or in combination of two or more.
The amount of the acid catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
酸触媒としては、例えば塩酸、硫酸、リン酸等の無機酸；シュウ酸、酢酸、クエン酸、酒石酸、安息香酸、パラトルエンスルホン酸等の有機酸；酢酸亜鉛、ホウ酸亜鉛等の有機酸塩；スルホン基やカルボン酸基を有するイオン交換樹脂等が挙げられる。これらの中でも、副反応による副生物の生成が抑制されると同時に、反応終了後、水洗処理などにより、容易に脱触媒を行うことができる点で、シュウ酸、塩酸、硫酸、パラトルエンスルホン酸が好ましい。これらの酸触媒は１種を単独で用いてもよく２種以上を併用してもよい。
酸触媒の使用量は、例えば、ビフェニル化合物１００質量部に対して０．０１～１００質量部である。 Typically, a biphenyl compound and a hydroxy compound are reacted in the presence of an acid catalyst. By using an acid catalyst, the reaction between the biphenyl compound and the hydroxy compound proceeds easily.
Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as oxalic acid, acetic acid, citric acid, tartaric acid, benzoic acid, and paratoluenesulfonic acid; and organic acid salts such as zinc acetate and zinc borate. ; Examples include ion exchange resins having sulfone groups and carboxylic acid groups. Among these, oxalic acid, hydrochloric acid, sulfuric acid, and para-toluenesulfonic acid are useful because they suppress the generation of byproducts due to side reactions and at the same time, they can be easily decatalyzed by washing with water after the reaction. is preferred. These acid catalysts may be used alone or in combination of two or more.
The amount of the acid catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
ビフェニル化合物とヒドロキシ化合物とを反応させる際、必要に応じて、助触媒を用いてもよい。
助触媒としては、例えばメチルメルカプタン、エチルメルカプタン、ノルマルプロピルメルカプタン、イソプロピルメルカプタン、ターシャリーブチルメルカプタン、ステアリルメルカプタン、ドデシルメルカプタン等のメルカプタン類が挙げられる。これらの助触媒は１種を単独で用いてもよく２種以上を併用してもよい。
助触媒の使用量は、例えば、ビフェニル化合物１００質量部に対して０．０１～１００質量部である。 When reacting a biphenyl compound and a hydroxy compound, a co-catalyst may be used if necessary.
Examples of the co-catalyst include mercaptans such as methyl mercaptan, ethyl mercaptan, normal propyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, stearyl mercaptan, and dodecyl mercaptan. These promoters may be used alone or in combination of two or more.
The amount of co-catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
助触媒としては、例えばメチルメルカプタン、エチルメルカプタン、ノルマルプロピルメルカプタン、イソプロピルメルカプタン、ターシャリーブチルメルカプタン、ステアリルメルカプタン、ドデシルメルカプタン等のメルカプタン類が挙げられる。これらの助触媒は１種を単独で用いてもよく２種以上を併用してもよい。
助触媒の使用量は、例えば、ビフェニル化合物１００質量部に対して０．０１～１００質量部である。 When reacting a biphenyl compound and a hydroxy compound, a co-catalyst may be used if necessary.
Examples of the co-catalyst include mercaptans such as methyl mercaptan, ethyl mercaptan, normal propyl mercaptan, isopropyl mercaptan, tert-butyl mercaptan, stearyl mercaptan, and dodecyl mercaptan. These promoters may be used alone or in combination of two or more.
The amount of co-catalyst used is, for example, 0.01 to 100 parts by weight per 100 parts by weight of the biphenyl compound.
工程Ａは、通常のノボラック型フェノール樹脂の製造方法と同様の方法で実施できる。
例えば、反応容器にビフェニル化合物、ヒドロキシ化合物、酸触媒、溶媒、必要に応じて助触媒を仕込み、任意の反応温度を任意の反応時間保持することで、化合物（１－１）を含む生成物が得られる。
溶媒としては、例えばイオン交換水等の水；ジエチルエーテル、シクロペンチルメチルエーテル、メタノール、エタノール、ベンゼン、トルエン、キシレン等の有機溶剤が挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。
反応温度は、例えば１０～１５０℃である。反応時間は、例えば０．５～４８時間である。
反応終了後、必要に応じて、抽出、水洗、濃縮、再結晶等の処理を行ってもよい。 Step A can be carried out in the same manner as the usual method for producing novolac type phenolic resin.
For example, by charging a biphenyl compound, a hydroxy compound, an acid catalyst, a solvent, and, if necessary, a co-catalyst into a reaction vessel and maintaining a desired reaction temperature for a desired reaction time, a product containing compound (1-1) can be produced. can get.
Examples of the solvent include water such as ion-exchanged water; organic solvents such as diethyl ether, cyclopentyl methyl ether, methanol, ethanol, benzene, toluene, and xylene. These may be used alone or in combination of two or more.
The reaction temperature is, for example, 10 to 150°C. The reaction time is, for example, 0.5 to 48 hours.
After the reaction is completed, treatments such as extraction, water washing, concentration, and recrystallization may be performed as necessary.
例えば、反応容器にビフェニル化合物、ヒドロキシ化合物、酸触媒、溶媒、必要に応じて助触媒を仕込み、任意の反応温度を任意の反応時間保持することで、化合物（１－１）を含む生成物が得られる。
溶媒としては、例えばイオン交換水等の水；ジエチルエーテル、シクロペンチルメチルエーテル、メタノール、エタノール、ベンゼン、トルエン、キシレン等の有機溶剤が挙げられる。これらは１種を単独で用いてもよく２種以上を併用してもよい。
反応温度は、例えば１０～１５０℃である。反応時間は、例えば０．５～４８時間である。
反応終了後、必要に応じて、抽出、水洗、濃縮、再結晶等の処理を行ってもよい。 Step A can be carried out in the same manner as the usual method for producing novolac type phenolic resin.
For example, by charging a biphenyl compound, a hydroxy compound, an acid catalyst, a solvent, and, if necessary, a co-catalyst into a reaction vessel and maintaining a desired reaction temperature for a desired reaction time, a product containing compound (1-1) can be produced. can get.
Examples of the solvent include water such as ion-exchanged water; organic solvents such as diethyl ether, cyclopentyl methyl ether, methanol, ethanol, benzene, toluene, and xylene. These may be used alone or in combination of two or more.
The reaction temperature is, for example, 10 to 150°C. The reaction time is, for example, 0.5 to 48 hours.
After the reaction is completed, treatments such as extraction, water washing, concentration, and recrystallization may be performed as necessary.
（工程Ｂ）
化合物（１－１）の水酸基に１以上のオキシアルキレン基（（ＯＲ３）ｃ、（ＯＲ３）ｄ）を付加することで、前記式（１）中のｃおよびｄの少なくとも一方が１以上である化合物（以下、「化合物（１－２）」とも記す。）が得られる。 (Process B)
By adding one or more oxyalkylene groups ((OR 3 ) c , (OR 3 ) d ) to the hydroxyl group of compound (1-1), at least one of c and d in the formula (1) is one or more. A compound (hereinafter also referred to as "compound (1-2)") is obtained.
化合物（１－１）の水酸基に１以上のオキシアルキレン基（（ＯＲ３）ｃ、（ＯＲ３）ｄ）を付加することで、前記式（１）中のｃおよびｄの少なくとも一方が１以上である化合物（以下、「化合物（１－２）」とも記す。）が得られる。 (Process B)
By adding one or more oxyalkylene groups ((OR 3 ) c , (OR 3 ) d ) to the hydroxyl group of compound (1-1), at least one of c and d in the formula (1) is one or more. A compound (hereinafter also referred to as "compound (1-2)") is obtained.
１以上のオキシアルキレン基の付加方法としては、公知の方法を用いることができる。例えば、化合物（１－１）と、エチレンオキサイド等のアルキレンオキサイドとを反応させる方法が挙げられる。
As a method for adding one or more oxyalkylene groups, known methods can be used. For example, a method of reacting the compound (1-1) with an alkylene oxide such as ethylene oxide may be mentioned.
〔光学部材（２）〕
本発明の光学部材の他の一態様として、下記式（２）で表される化合物（以下、「化合物（２）」とも記す。）を含む硬化性組成物（以下、「光学部材形成材料（２）」とも記す。）の硬化物を含む光学部材（以下、「光学部材（２）」とも記す。）が挙げられる。
硬化物は、化合物（２）に基づく構成単位を有する。化合物（２）に基づく構成単位は、前記した構造（ｉ）を含む。 [Optical member (2)]
Another embodiment of the optical member of the present invention is a curable composition (hereinafter referred to as "optical member forming material") containing a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"). Examples include optical members (hereinafter also referred to as "optical members (2)") containing a cured product of (also referred to as "optical members (2)").
The cured product has a structural unit based on compound (2). The structural unit based on compound (2) includes the structure (i) described above.
本発明の光学部材の他の一態様として、下記式（２）で表される化合物（以下、「化合物（２）」とも記す。）を含む硬化性組成物（以下、「光学部材形成材料（２）」とも記す。）の硬化物を含む光学部材（以下、「光学部材（２）」とも記す。）が挙げられる。
硬化物は、化合物（２）に基づく構成単位を有する。化合物（２）に基づく構成単位は、前記した構造（ｉ）を含む。 [Optical member (2)]
Another embodiment of the optical member of the present invention is a curable composition (hereinafter referred to as "optical member forming material") containing a compound represented by the following formula (2) (hereinafter also referred to as "compound (2)"). Examples include optical members (hereinafter also referred to as "optical members (2)") containing a cured product of (also referred to as "optical members (2)").
The cured product has a structural unit based on compound (2). The structural unit based on compound (2) includes the structure (i) described above.
式（２）中、Ｒ１、ａ、ｂ、Ｒ２、ｃ、ｄ、Ｒ３、ｅ、ｆ、ｇ、ｈおよびＲ４はそれぞれ前記したとおりである。
Ｘは、重合性官能基もしくは反応性官能基を含む１価基（以下、「基（ｘ）」とも記す。）、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は基（ｘ）である。
化合物（２）は、１個以上の重合性官能基または反応性官能基を持つので、単独でまたは硬化剤により硬化させることができる。 In formula (2), R 1 , a, b, R 2 , c, d, R 3 , e, f, g, h and R 4 are each as described above.
X is a monovalent group containing a polymerizable functional group or a reactive functional group (hereinafter also referred to as "group (x)"), or a hydrogen atom, and (e+f) X's may be the same or different. Often, at least one of the (e+f) X's is a group (x).
Since compound (2) has one or more polymerizable functional groups or reactive functional groups, it can be cured alone or with a curing agent.
Ｘは、重合性官能基もしくは反応性官能基を含む１価基（以下、「基（ｘ）」とも記す。）、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は基（ｘ）である。
化合物（２）は、１個以上の重合性官能基または反応性官能基を持つので、単独でまたは硬化剤により硬化させることができる。 In formula (2), R 1 , a, b, R 2 , c, d, R 3 , e, f, g, h and R 4 are each as described above.
X is a monovalent group containing a polymerizable functional group or a reactive functional group (hereinafter also referred to as "group (x)"), or a hydrogen atom, and (e+f) X's may be the same or different. Often, at least one of the (e+f) X's is a group (x).
Since compound (2) has one or more polymerizable functional groups or reactive functional groups, it can be cured alone or with a curing agent.
基（ｘ）における重合性官能基としては、重合可能なものであれば特に制限はなく、例えば（メタ）アクリロイル基等が挙げられる。（メタ）アクリロイル基はアクリロイル基またはメタクリロイル基を意味する。
基（ｘ）における反応性官能基としては、例えばエポキシ基、酸無水物基、アミノ基等が挙げられる。
基（ｘ）が有する重合性官能基または反応性官能基は１個でも２個以上でもよいが、典型的には１個である。
重合性官能基または反応性官能基は、Ｘに隣接する酸素原子に直接結合していてもよく、連結基を介して結合していてもよい。 The polymerizable functional group in group (x) is not particularly limited as long as it is polymerizable, and examples include (meth)acryloyl groups. A (meth)acryloyl group means an acryloyl group or a methacryloyl group.
Examples of the reactive functional group in the group (x) include an epoxy group, an acid anhydride group, and an amino group.
The number of polymerizable functional groups or reactive functional groups possessed by the group (x) may be one or two or more, but typically it is one.
The polymerizable functional group or reactive functional group may be bonded directly to the oxygen atom adjacent to X, or may be bonded via a linking group.
基（ｘ）における反応性官能基としては、例えばエポキシ基、酸無水物基、アミノ基等が挙げられる。
基（ｘ）が有する重合性官能基または反応性官能基は１個でも２個以上でもよいが、典型的には１個である。
重合性官能基または反応性官能基は、Ｘに隣接する酸素原子に直接結合していてもよく、連結基を介して結合していてもよい。 The polymerizable functional group in group (x) is not particularly limited as long as it is polymerizable, and examples include (meth)acryloyl groups. A (meth)acryloyl group means an acryloyl group or a methacryloyl group.
Examples of the reactive functional group in the group (x) include an epoxy group, an acid anhydride group, and an amino group.
The number of polymerizable functional groups or reactive functional groups possessed by the group (x) may be one or two or more, but typically it is one.
The polymerizable functional group or reactive functional group may be bonded directly to the oxygen atom adjacent to X, or may be bonded via a linking group.
基（ｘ）としては、例えば、－Ｘ２－Ｘ１で表される基が挙げられる。Ｘ１は、重合性官能基または反応性官能基であり、Ｘ２は、単結合または２価の連結基である。
Ｘ２における２価の連結基としては、例えば、置換基を有していてもよい２価の炭化水素基、置換基を有していてもよい２価の炭化水素基の末端または／および炭素原子間にエーテル性酸素原子を含む基等が挙げられる。
２価の炭化水素基としては、例えばアルキレン基、シクロアルキレン基、アリーレン基およびそれらの２以上の組み合わせからなる基が挙げられる。アルキレン基としては、Ｒ３におけるアルキレン基と同様のものが挙げられる。アルキレン基が有していてもよい置換基としては、例えば水酸基、シアノ基、ハロゲン原子が挙げられる。シクロアルキレン基の炭素数は、例えば６～８である。シクロアルキレン基が有していてもよい置換基としては、例えばアルキル基、水酸基、シアノ基、ハロゲン原子が挙げられる。アリーレン基としては、例えばフェニレン基、ナフチレン基、フェナントリレン基、アントリレン基、４，４’－ビフェニル－ジイル基が挙げられる。アリーレン基が有していてもよい置換基としては、例えばアルキル基、水酸基、シアノ基、ハロゲン原子が挙げられる。
Ｘ２としては、置換基として水酸基を有するものが好ましい。Ｘ２が水酸基を有していれば、化合物（２）を用いた硬化物の耐熱性や機械強度がより優れる傾向がある。これは、水酸基が存在することで、水素結合による分子間力が得られ、分子の凝集力が高まるためと考えられる。また、この水素結合は、ガラスやポリエステル等の無機または有機物（例えばフィルム、レンズ、など）に対する密着性向上にも寄与する。 Examples of the group (x) include a group represented by -X 2 -X 1 . X 1 is a polymerizable functional group or a reactive functional group, and X 2 is a single bond or a divalent linking group.
The divalent linking group in X 2 is, for example, a divalent hydrocarbon group that may have a substituent, a terminal of a divalent hydrocarbon group that may have a substituent, or/and a carbon Examples include groups containing etheric oxygen atoms between atoms.
Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, an arylene group, and a group consisting of a combination of two or more thereof. Examples of the alkylene group include those similar to the alkylene group for R3 . Examples of the substituent that the alkylene group may have include a hydroxyl group, a cyano group, and a halogen atom. The number of carbon atoms in the cycloalkylene group is, for example, 6 to 8. Examples of the substituent that the cycloalkylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom. Examples of the arylene group include phenylene group, naphthylene group, phenanthrylene group, anthrylene group, and 4,4'-biphenyl-diyl group. Examples of substituents that the arylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom.
X 2 is preferably one having a hydroxyl group as a substituent. If X 2 has a hydroxyl group, the cured product using compound (2) tends to have better heat resistance and mechanical strength. This is thought to be because the presence of hydroxyl groups provides intermolecular force due to hydrogen bonds, increasing the cohesive force of molecules. Moreover, this hydrogen bond also contributes to improving the adhesion to inorganic or organic substances (for example, films, lenses, etc.) such as glass and polyester.
Ｘ２における２価の連結基としては、例えば、置換基を有していてもよい２価の炭化水素基、置換基を有していてもよい２価の炭化水素基の末端または／および炭素原子間にエーテル性酸素原子を含む基等が挙げられる。
２価の炭化水素基としては、例えばアルキレン基、シクロアルキレン基、アリーレン基およびそれらの２以上の組み合わせからなる基が挙げられる。アルキレン基としては、Ｒ３におけるアルキレン基と同様のものが挙げられる。アルキレン基が有していてもよい置換基としては、例えば水酸基、シアノ基、ハロゲン原子が挙げられる。シクロアルキレン基の炭素数は、例えば６～８である。シクロアルキレン基が有していてもよい置換基としては、例えばアルキル基、水酸基、シアノ基、ハロゲン原子が挙げられる。アリーレン基としては、例えばフェニレン基、ナフチレン基、フェナントリレン基、アントリレン基、４，４’－ビフェニル－ジイル基が挙げられる。アリーレン基が有していてもよい置換基としては、例えばアルキル基、水酸基、シアノ基、ハロゲン原子が挙げられる。
Ｘ２としては、置換基として水酸基を有するものが好ましい。Ｘ２が水酸基を有していれば、化合物（２）を用いた硬化物の耐熱性や機械強度がより優れる傾向がある。これは、水酸基が存在することで、水素結合による分子間力が得られ、分子の凝集力が高まるためと考えられる。また、この水素結合は、ガラスやポリエステル等の無機または有機物（例えばフィルム、レンズ、など）に対する密着性向上にも寄与する。 Examples of the group (x) include a group represented by -X 2 -X 1 . X 1 is a polymerizable functional group or a reactive functional group, and X 2 is a single bond or a divalent linking group.
The divalent linking group in X 2 is, for example, a divalent hydrocarbon group that may have a substituent, a terminal of a divalent hydrocarbon group that may have a substituent, or/and a carbon Examples include groups containing etheric oxygen atoms between atoms.
Examples of the divalent hydrocarbon group include an alkylene group, a cycloalkylene group, an arylene group, and a group consisting of a combination of two or more thereof. Examples of the alkylene group include those similar to the alkylene group for R3 . Examples of the substituent that the alkylene group may have include a hydroxyl group, a cyano group, and a halogen atom. The number of carbon atoms in the cycloalkylene group is, for example, 6 to 8. Examples of the substituent that the cycloalkylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom. Examples of the arylene group include phenylene group, naphthylene group, phenanthrylene group, anthrylene group, and 4,4'-biphenyl-diyl group. Examples of substituents that the arylene group may have include an alkyl group, a hydroxyl group, a cyano group, and a halogen atom.
X 2 is preferably one having a hydroxyl group as a substituent. If X 2 has a hydroxyl group, the cured product using compound (2) tends to have better heat resistance and mechanical strength. This is thought to be because the presence of hydroxyl groups provides intermolecular force due to hydrogen bonds, increasing the cohesive force of molecules. Moreover, this hydrogen bond also contributes to improving the adhesion to inorganic or organic substances (for example, films, lenses, etc.) such as glass and polyester.
基（ｘ）の具体例としては、グリシジル基、－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１、（メタ）アクリロイル基、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピル基（－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ－Ｃ（＝Ｏ）－Ｃ（Ｒ）＝ＣＨ２）、－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｃ（＝Ｏ）－Ｃ（Ｒ）＝ＣＨ２、トリメリット酸無水物基（下記式（ｘ－１）で表される基）、アミノ基等が挙げられる。Ｐｈはフェニレン基であり、Ｙ１はグリシジル基であり、Ｒは水素原子またはメチル基である。ｎは特に限定されないが、例えば１～１０の整数である。
Specific examples of the group (x) include glycidyl group, -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 , (meth)acryloyl group, 2-hydroxy-3-(meth)acryloyloxypropyl group (-CH 2 -CH(OH)-CH 2 -O-C(=O)-C (R)=CH 2 ), -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -C(=O)-C(R)=CH 2 , a trimellitic anhydride group (a group represented by the following formula (x-1)), an amino group, and the like. Ph is a phenylene group, Y1 is a glycidyl group, and R is a hydrogen atom or a methyl group. Although n is not particularly limited, it is, for example, an integer from 1 to 10.
基（ｘ）としては、硬化物が耐熱性や機械強度に優れ、光学部材としての有用性に優れる点で、２－ヒドロキシ－３－（メタ）アクリロイルオキシプロピル基が好ましい。
As the group (x), a 2-hydroxy-3-(meth)acryloyloxypropyl group is preferred since the cured product has excellent heat resistance and mechanical strength and is useful as an optical member.
光学部材形成材料（２）は、必要に応じて、本発明の効果を損なわない範囲で、化合物（２）以外の他の成分をさらに含んでいてもよい。他の成分としては、例えば、化合物（２）以外の重合性官能基または反応性官能基を持つ化合物、硬化剤（架橋剤、重合開始剤等）、硬化促進剤、溶剤、着色剤、無機充填剤、有機充填剤、酸化防止剤、その他の各種の添加剤が挙げられる。他の成分は１種を単独で用いてもよく２種以上を併用してもよい。
The optical member forming material (2) may further contain other components other than the compound (2), if necessary, within a range that does not impair the effects of the present invention. Other components include, for example, a compound having a polymerizable functional group or a reactive functional group other than compound (2), a curing agent (crosslinking agent, polymerization initiator, etc.), a curing accelerator, a solvent, a coloring agent, an inorganic filler. additives, organic fillers, antioxidants, and other various additives. As for the other components, one kind may be used alone or two or more kinds may be used in combination.
基（ｘ）が（メタ）アクリロイル基等の重合性官能基を有する場合、光学部材形成材料（２）は、重合開始剤（光重合開始剤、熱重合開始剤等）を含むことが好ましい。
When the group (x) has a polymerizable functional group such as a (meth)acryloyl group, the optical member forming material (2) preferably contains a polymerization initiator (photopolymerization initiator, thermal polymerization initiator, etc.).
基（ｘ）が反応性官能基を有する場合、光学部材形成材料（２）は、基（ｘ）の反応性官能基と反応し得る官能基を２以上有する架橋剤を含むことが好ましい。反応性官能基がエポキシ基である場合、エポキシ基と反応し得る官能基としては、アミノ基、酸無水物基、水酸基等が挙げられる。反応性官能基が酸無水物基である場合、酸無水物基と反応し得る官能基としては、アミノ基、水酸基等が挙げられる。反応性官能基がアミノ基である場合、アミノ基と反応し得る官能基としては、酸無水物基等が挙げられる。
When the group (x) has a reactive functional group, the optical member forming material (2) preferably contains a crosslinking agent having two or more functional groups that can react with the reactive functional group of the group (x). When the reactive functional group is an epoxy group, examples of the functional group that can react with the epoxy group include an amino group, an acid anhydride group, and a hydroxyl group. When the reactive functional group is an acid anhydride group, examples of the functional group that can react with the acid anhydride group include an amino group and a hydroxyl group. When the reactive functional group is an amino group, examples of the functional group that can react with the amino group include acid anhydride groups.
基（ｘ）がエポキシ基を有する場合に用いられる架橋剤としては、例えば、アミン類、酸無水物類、フェノール樹脂等のエポキシ硬化剤が挙げられる。必要に応じて、トリフェニルホスフィン類やイミダゾール類等の硬化促進剤を併用してもよい。
Examples of the crosslinking agent used when the group (x) has an epoxy group include epoxy curing agents such as amines, acid anhydrides, and phenolic resins. If necessary, a curing accelerator such as triphenylphosphine or imidazole may be used in combination.
基（ｘ）が酸無水物基を有する場合に用いられる架橋剤としては、例えば、ジアミンが挙げられる。この場合、化合物（２）とジアミンとの反応さによりポリイミドが生成する。ジアミンとしては、例えば１，３－フェニレンジアミン、４，４’－ジアミノジフェニルエーテル、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、ジアミン化合物、ジエチレングリコールビス（３－アミノプロピル）エーテル、９，９’－ビス（４－アミノフェニル）フルオレンが挙げられる。ジアミンは１種を単独で用いてもよく２種以上を併用してもよい。
Examples of the crosslinking agent used when the group (x) has an acid anhydride group include diamine. In this case, polyimide is produced by the reaction between compound (2) and diamine. Examples of diamines include 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, diamine compounds, diethylene glycol bis(3-aminopropyl) Examples include ether and 9,9'-bis(4-aminophenyl)fluorene. One type of diamine may be used alone or two or more types may be used in combination.
＜光学部材（２）の製造方法＞
光学部材（２）は、光学部材形成材料（２）を硬化することにより製造できる。
光学部材形成材料（２）を硬化する前に、光学部材形成材料（２）を製造してもよい。光学部材形成材料（２）の製造方法については後で詳しく説明する。 <Method for manufacturing optical member (2)>
The optical member (2) can be manufactured by curing the optical member forming material (2).
The optical member forming material (2) may be manufactured before the optical member forming material (2) is cured. The method for manufacturing the optical member forming material (2) will be explained in detail later.
光学部材（２）は、光学部材形成材料（２）を硬化することにより製造できる。
光学部材形成材料（２）を硬化する前に、光学部材形成材料（２）を製造してもよい。光学部材形成材料（２）の製造方法については後で詳しく説明する。 <Method for manufacturing optical member (2)>
The optical member (2) can be manufactured by curing the optical member forming material (2).
The optical member forming material (2) may be manufactured before the optical member forming material (2) is cured. The method for manufacturing the optical member forming material (2) will be explained in detail later.
光学部材形成材料（２）の硬化方法は特に限定されず、基（ｘ）が有する重合性官能基または反応性官能基の種類に応じて公知の方法を適用できる。例えば基（ｘ）が重合性官能基を有する場合、光学部材形成材料（２）に光や熱を加えることで、化合物（２）等を重合させ、硬化物とすることができる。
光学部材形成材料（２）を硬化する際に、光学部材形成材料（２）を、目的の光学部材の形状に成形してもよい。光学部材形成材料（２）を硬化した後に、硬化物を、目的の光学部材の形状に成形してもよい。 The method for curing the optical member forming material (2) is not particularly limited, and known methods can be applied depending on the type of polymerizable functional group or reactive functional group that the group (x) has. For example, when the group (x) has a polymerizable functional group, by applying light or heat to the optical member forming material (2), the compound (2) etc. can be polymerized to form a cured product.
When curing the optical member forming material (2), the optical member forming material (2) may be molded into the shape of the desired optical member. After curing the optical member forming material (2), the cured product may be molded into the shape of the desired optical member.
光学部材形成材料（２）を硬化する際に、光学部材形成材料（２）を、目的の光学部材の形状に成形してもよい。光学部材形成材料（２）を硬化した後に、硬化物を、目的の光学部材の形状に成形してもよい。 The method for curing the optical member forming material (2) is not particularly limited, and known methods can be applied depending on the type of polymerizable functional group or reactive functional group that the group (x) has. For example, when the group (x) has a polymerizable functional group, by applying light or heat to the optical member forming material (2), the compound (2) etc. can be polymerized to form a cured product.
When curing the optical member forming material (2), the optical member forming material (2) may be molded into the shape of the desired optical member. After curing the optical member forming material (2), the cured product may be molded into the shape of the desired optical member.
＜光学部材形成材料（２）の製造方法＞
光学部材形成材料（２）は、例えば、化合物（２）を製造し、必要に応じて他の成分を混合することにより製造できる。
化合物（２）は、例えば、以下の工程Ｃを有する製造方法により製造できる。
工程Ｃ：式（２）中のＯＸが全てＯＨである化合物、つまり化合物（１）のＯＨの少なくとも一部に、基（ｘ）を付加する工程。 <Method for manufacturing optical member forming material (2)>
Optical member forming material (2) can be manufactured, for example, by manufacturing compound (2) and mixing other components as necessary.
Compound (2) can be produced, for example, by a production method including Step C below.
Step C: A step of adding group (x) to at least a portion of the OH of compound (1), which is a compound in which all OX in formula (2) are OH.
光学部材形成材料（２）は、例えば、化合物（２）を製造し、必要に応じて他の成分を混合することにより製造できる。
化合物（２）は、例えば、以下の工程Ｃを有する製造方法により製造できる。
工程Ｃ：式（２）中のＯＸが全てＯＨである化合物、つまり化合物（１）のＯＨの少なくとも一部に、基（ｘ）を付加する工程。 <Method for manufacturing optical member forming material (2)>
Optical member forming material (2) can be manufactured, for example, by manufacturing compound (2) and mixing other components as necessary.
Compound (2) can be produced, for example, by a production method including Step C below.
Step C: A step of adding group (x) to at least a portion of the OH of compound (1), which is a compound in which all OX in formula (2) are OH.
（工程Ｃ）
工程Ｃは、基（ｘ）の構造に応じて、公知の方法を用いて実施できる。
例えば、基（ｘ）がグリシジル基の場合、化合物（１）のＯＨにエピハロヒドリン（例えばエピクロルヒドリン）を反応させる方法（以下、「方法１」とも記す。）が挙げられる。
基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１の場合、方法１において、エピハロヒドリンの代わりに、ＯＨ１モルに対して（ｎ＋１）モルのビスフェノールＡ型エポキシ化合物（ＨＯ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１）を反応させればよい。
基（ｘ）が（メタ）アクリロイル基である場合、化合物（１）のＯＨに（メタ）アクリル酸、（メタ）アクリル酸無水物または（メタ）アクリル酸ハロゲン化物を反応させる方法（以下、「方法２」とも記す。）が挙げられる。
基（ｘ）が２－（メタ）アクリロイルオキシ－２－ヒドロキシエチル基である場合、上述の方法１によって基（ｘ）がグリシジル基である化合物を得、この化合物のグリシジル基に（メタ）アクリル酸、（メタ）アクリル酸無水物または（メタ）アクリル酸ハロゲン化物を反応させる方法（以下、「方法３」とも記す。）が挙げられる。
基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｃ（＝Ｏ）－Ｃ（Ｒ）＝ＣＨ２の場合、方法３において、基（ｘ）がグリシジル基である化合物を得る代わりに、基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１である化合物を得ればよい。
基（ｘ）がトリメリット酸無水物基である場合、化合物（１）のＯＨに無水トリメリット酸または無水トリメリット酸ハライドを反応させる方法（以下、「方法４」とも記す。）が挙げられる。 (Process C)
Step C can be carried out using a known method depending on the structure of group (x).
For example, when the group (x) is a glycidyl group, a method (hereinafter also referred to as "method 1") in which the OH of compound (1) is reacted with epihalohydrin (e.g., epichlorohydrin) can be used.
Group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 In this case, in Method 1, instead of epihalohydrin, (n+1) mol of bisphenol A type epoxy compound (HO-Ph-C(CH 3 ) 2 -Ph-O-Y 1 ) is reacted with respect to 1 mol of OH. Bye.
When the group (x) is a (meth)acryloyl group, a method of reacting the OH of compound (1) with (meth)acrylic acid, (meth)acrylic anhydride or (meth)acrylic acid halide (hereinafter referred to as " (also referred to as "Method 2").
When the group (x) is a 2-(meth)acryloyloxy-2-hydroxyethyl group, a compound in which the group (x) is a glycidyl group is obtained by the above method 1, and (meth)acrylic is added to the glycidyl group of this compound. A method of reacting an acid, (meth)acrylic anhydride, or (meth)acrylic acid halide (hereinafter also referred to as "Method 3") can be mentioned.
When the group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -C(=O)-C(R)=CH 2 , in method 3, instead of obtaining a compound in which the group (x) is a glycidyl group, the group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 may be obtained.
When the group (x) is a trimellitic anhydride group, a method of reacting OH of compound (1) with trimellitic anhydride or trimellitic anhydride halide (hereinafter also referred to as "Method 4") can be mentioned. .
工程Ｃは、基（ｘ）の構造に応じて、公知の方法を用いて実施できる。
例えば、基（ｘ）がグリシジル基の場合、化合物（１）のＯＨにエピハロヒドリン（例えばエピクロルヒドリン）を反応させる方法（以下、「方法１」とも記す。）が挙げられる。
基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１の場合、方法１において、エピハロヒドリンの代わりに、ＯＨ１モルに対して（ｎ＋１）モルのビスフェノールＡ型エポキシ化合物（ＨＯ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１）を反応させればよい。
基（ｘ）が（メタ）アクリロイル基である場合、化合物（１）のＯＨに（メタ）アクリル酸、（メタ）アクリル酸無水物または（メタ）アクリル酸ハロゲン化物を反応させる方法（以下、「方法２」とも記す。）が挙げられる。
基（ｘ）が２－（メタ）アクリロイルオキシ－２－ヒドロキシエチル基である場合、上述の方法１によって基（ｘ）がグリシジル基である化合物を得、この化合物のグリシジル基に（メタ）アクリル酸、（メタ）アクリル酸無水物または（メタ）アクリル酸ハロゲン化物を反応させる方法（以下、「方法３」とも記す。）が挙げられる。
基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｃ（＝Ｏ）－Ｃ（Ｒ）＝ＣＨ２の場合、方法３において、基（ｘ）がグリシジル基である化合物を得る代わりに、基（ｘ）が－［Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－ＣＨ２－ＣＨ（ＯＨ）－ＣＨ２－Ｏ］ｎ－Ｐｈ－Ｃ（ＣＨ３）２－Ｐｈ－Ｏ－Ｙ１である化合物を得ればよい。
基（ｘ）がトリメリット酸無水物基である場合、化合物（１）のＯＨに無水トリメリット酸または無水トリメリット酸ハライドを反応させる方法（以下、「方法４」とも記す。）が挙げられる。 (Process C)
Step C can be carried out using a known method depending on the structure of group (x).
For example, when the group (x) is a glycidyl group, a method (hereinafter also referred to as "method 1") in which the OH of compound (1) is reacted with epihalohydrin (e.g., epichlorohydrin) can be used.
Group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 In this case, in Method 1, instead of epihalohydrin, (n+1) mol of bisphenol A type epoxy compound (HO-Ph-C(CH 3 ) 2 -Ph-O-Y 1 ) is reacted with respect to 1 mol of OH. Bye.
When the group (x) is a (meth)acryloyl group, a method of reacting the OH of compound (1) with (meth)acrylic acid, (meth)acrylic anhydride or (meth)acrylic acid halide (hereinafter referred to as " (also referred to as "Method 2").
When the group (x) is a 2-(meth)acryloyloxy-2-hydroxyethyl group, a compound in which the group (x) is a glycidyl group is obtained by the above method 1, and (meth)acrylic is added to the glycidyl group of this compound. A method of reacting an acid, (meth)acrylic anhydride, or (meth)acrylic acid halide (hereinafter also referred to as "Method 3") can be mentioned.
When the group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -C(=O)-C(R)=CH 2 , in method 3, instead of obtaining a compound in which the group (x) is a glycidyl group, the group (x) is -[Ph-C(CH 3 ) 2 -Ph-O-CH 2 -CH(OH)-CH 2 -O] n -Ph-C(CH 3 ) 2 -Ph-O-Y 1 may be obtained.
When the group (x) is a trimellitic anhydride group, a method of reacting OH of compound (1) with trimellitic anhydride or trimellitic anhydride halide (hereinafter also referred to as "Method 4") can be mentioned. .
方法１において、化合物（１）のＯＨに対するエピハロヒドリンのモル比（ＯＨ／エピハロヒドリン比）は、最も一般的なエポキシ樹脂であるビスフェノールＡ型エポキシ樹脂を、ビスフェノールＡとエピクロルヒドリンから製造する際と同様のモル比であってよい。
ＯＨ／エピクロルヒドリン比は、０．０２～０．３３が好ましく、０．１０～０．２０がより好ましい。
化合物（１）のＯＨ１モルに対して多量のエピクロルヒドリンを用いた場合（ＯＨ／エピクロルヒドリン比が小さい場合）には、ＯＨがグリシジルエーテル化された化合物が主成分として得られる。このモル比を大きくするに従い、ＯＨに付加したグリシジルエーテル化したエポキシ基が他のＯＨと反応し、高分子量化されるおそれがある。 In method 1, the molar ratio of epihalohydrin to OH of compound (1) (OH/epihalohydrin ratio) is the same molar ratio as when producing bisphenol A type epoxy resin, which is the most common epoxy resin, from bisphenol A and epichlorohydrin. It may be a ratio.
The OH/epichlorohydrin ratio is preferably 0.02 to 0.33, more preferably 0.10 to 0.20.
When a large amount of epichlorohydrin is used per mole of OH of compound (1) (when the OH/epichlorohydrin ratio is small), a compound in which OH is glycidyl etherified is obtained as a main component. As this molar ratio increases, there is a possibility that the glycidyl etherified epoxy group added to OH will react with other OH and the molecular weight will be increased.
ＯＨ／エピクロルヒドリン比は、０．０２～０．３３が好ましく、０．１０～０．２０がより好ましい。
化合物（１）のＯＨ１モルに対して多量のエピクロルヒドリンを用いた場合（ＯＨ／エピクロルヒドリン比が小さい場合）には、ＯＨがグリシジルエーテル化された化合物が主成分として得られる。このモル比を大きくするに従い、ＯＨに付加したグリシジルエーテル化したエポキシ基が他のＯＨと反応し、高分子量化されるおそれがある。 In method 1, the molar ratio of epihalohydrin to OH of compound (1) (OH/epihalohydrin ratio) is the same molar ratio as when producing bisphenol A type epoxy resin, which is the most common epoxy resin, from bisphenol A and epichlorohydrin. It may be a ratio.
The OH/epichlorohydrin ratio is preferably 0.02 to 0.33, more preferably 0.10 to 0.20.
When a large amount of epichlorohydrin is used per mole of OH of compound (1) (when the OH/epichlorohydrin ratio is small), a compound in which OH is glycidyl etherified is obtained as a main component. As this molar ratio increases, there is a possibility that the glycidyl etherified epoxy group added to OH will react with other OH and the molecular weight will be increased.
以上説明した本発明の光学部材は、構造（ｉ）を有することから、高い屈折率（例えば１．６２～１．７８の屈折率）を示す。
ここで、一般に、分子全体の分極が大きくなると、高屈折率を発現する傾向がある。分子全体の分極を大きくする手法の一つが、自由に動くことができる共役π電子を多くすることである。
構造（ｉ）中のビフェニル部位においては、２個のベンゼン環内に存在する１２個のπ電子がビフェニル部位全体の広範囲に共鳴している。このビフェニル部位にさらに、すくなくとも２個のベンゼン環が導入されることで、共役π電子の数が増大し、π電子が共鳴する範囲も広くなる。これにより、分子全体がより分極しやすくなり、高屈折率を発現すると考えられる。 Since the optical member of the present invention described above has the structure (i), it exhibits a high refractive index (for example, a refractive index of 1.62 to 1.78).
Here, in general, when the polarization of the entire molecule becomes large, a high refractive index tends to be exhibited. One way to increase the polarization of the entire molecule is to increase the number of freely movable conjugated π electrons.
In the biphenyl moiety in structure (i), the 12 π electrons present in the two benzene rings resonate over a wide range of the entire biphenyl moiety. By further introducing at least two benzene rings into this biphenyl moiety, the number of conjugated π electrons increases and the range in which π electrons resonate also becomes wider. It is thought that this makes the entire molecule more easily polarized and develops a high refractive index.
ここで、一般に、分子全体の分極が大きくなると、高屈折率を発現する傾向がある。分子全体の分極を大きくする手法の一つが、自由に動くことができる共役π電子を多くすることである。
構造（ｉ）中のビフェニル部位においては、２個のベンゼン環内に存在する１２個のπ電子がビフェニル部位全体の広範囲に共鳴している。このビフェニル部位にさらに、すくなくとも２個のベンゼン環が導入されることで、共役π電子の数が増大し、π電子が共鳴する範囲も広くなる。これにより、分子全体がより分極しやすくなり、高屈折率を発現すると考えられる。 Since the optical member of the present invention described above has the structure (i), it exhibits a high refractive index (for example, a refractive index of 1.62 to 1.78).
Here, in general, when the polarization of the entire molecule becomes large, a high refractive index tends to be exhibited. One way to increase the polarization of the entire molecule is to increase the number of freely movable conjugated π electrons.
In the biphenyl moiety in structure (i), the 12 π electrons present in the two benzene rings resonate over a wide range of the entire biphenyl moiety. By further introducing at least two benzene rings into this biphenyl moiety, the number of conjugated π electrons increases and the range in which π electrons resonate also becomes wider. It is thought that this makes the entire molecule more easily polarized and develops a high refractive index.
また、従来のフルオレン骨格を有するモノマーは、溶剤溶解性が低いという問題がある。溶剤溶解性が低いと、モノマーを溶解可能な溶剤の選択肢が限られる。よって、フルオレン骨格を有するモノマーでは、高品質の光学部材を汎用的な溶剤（例えばＮ－メチル－２－ピロリドン）で製造できず、実用性に劣る。
これに対し、本発明において、構造（ｉ）に対応する化合物（１）や化合物（２）は、溶剤溶解性に優れる。これらの化合物の優れた溶剤溶解性は、前記したビフェニル化合物の－Ｃ（Ｒ１）＝Ｏ由来の炭素原子に結合した２つのヒドロキシ化合物由来の部分が自由回転できるため、溶剤と相互作用しやすいことによるものと推定される。これらの化合物が溶剤溶解性に優れることから、汎用的な溶剤で高品質の光学部材を製造できる。 Further, conventional monomers having a fluorene skeleton have a problem of low solvent solubility. Low solvent solubility limits the choices of solvents that can dissolve the monomer. Therefore, monomers having a fluorene skeleton cannot be used to produce high-quality optical members using general-purpose solvents (eg, N-methyl-2-pyrrolidone), and are therefore less practical.
On the other hand, in the present invention, compound (1) and compound (2) corresponding to structure (i) have excellent solvent solubility. The excellent solvent solubility of these compounds is due to the fact that the two hydroxy compound-derived moieties bonded to the carbon atom derived from -C(R 1 )=O of the biphenyl compound described above can freely rotate, so they easily interact with solvents. It is presumed that this is due to the following. Since these compounds have excellent solvent solubility, high-quality optical members can be manufactured using general-purpose solvents.
これに対し、本発明において、構造（ｉ）に対応する化合物（１）や化合物（２）は、溶剤溶解性に優れる。これらの化合物の優れた溶剤溶解性は、前記したビフェニル化合物の－Ｃ（Ｒ１）＝Ｏ由来の炭素原子に結合した２つのヒドロキシ化合物由来の部分が自由回転できるため、溶剤と相互作用しやすいことによるものと推定される。これらの化合物が溶剤溶解性に優れることから、汎用的な溶剤で高品質の光学部材を製造できる。 Further, conventional monomers having a fluorene skeleton have a problem of low solvent solubility. Low solvent solubility limits the choices of solvents that can dissolve the monomer. Therefore, monomers having a fluorene skeleton cannot be used to produce high-quality optical members using general-purpose solvents (eg, N-methyl-2-pyrrolidone), and are therefore less practical.
On the other hand, in the present invention, compound (1) and compound (2) corresponding to structure (i) have excellent solvent solubility. The excellent solvent solubility of these compounds is due to the fact that the two hydroxy compound-derived moieties bonded to the carbon atom derived from -C(R 1 )=O of the biphenyl compound described above can freely rotate, so they easily interact with solvents. It is presumed that this is due to the following. Since these compounds have excellent solvent solubility, high-quality optical members can be manufactured using general-purpose solvents.
本発明の光学部材の具体例としては、ＣＭＯＳイメージセンサー用マイクロレンズ、タッチパネル用インデックスマッチング材、液晶用ブラックマトリックス、光学用接着材、透明ポリイミド、ＬＥＤ用透明電極等が挙げられる。
Specific examples of the optical member of the present invention include microlenses for CMOS image sensors, index matching materials for touch panels, black matrices for liquid crystals, optical adhesives, transparent polyimides, transparent electrodes for LEDs, and the like.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の記載によっては限定されない。以下において「％」は、特に言及がない場合は、「質量％」を示す。
Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the following description. In the following, "%" indicates "mass%" unless otherwise mentioned.
〔測定方法〕
＜ＮＭＲ測定＞
試料（各例の化合物）の７．７％ｄ－ジメチルスルホキシド（ＤＭＳＯ）溶液を調製し、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲを測定した。内部標準としてはテトラメチルシランを用いた。
使用機器：ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製 ＥＣＺ－５００Ｒ 〔Measuring method〕
<NMR measurement>
A 7.7% d-dimethylsulfoxide (DMSO) solution of the sample (compound of each example) was prepared, and 1 H-NMR and 13 C-NMR were measured. Tetramethylsilane was used as an internal standard.
Equipment used: JEOL RESONANCE ECZ-500R
＜ＮＭＲ測定＞
試料（各例の化合物）の７．７％ｄ－ジメチルスルホキシド（ＤＭＳＯ）溶液を調製し、１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲを測定した。内部標準としてはテトラメチルシランを用いた。
使用機器：ＪＥＯＬ ＲＥＳＯＮＡＮＣＥ社製 ＥＣＺ－５００Ｒ 〔Measuring method〕
<NMR measurement>
A 7.7% d-dimethylsulfoxide (DMSO) solution of the sample (compound of each example) was prepared, and 1 H-NMR and 13 C-NMR were measured. Tetramethylsilane was used as an internal standard.
Equipment used: JEOL RESONANCE ECZ-500R
＜ＦＤ－ＭＳ（電界脱離質量分析）＞
試料の０．２％テトラヒドロフラン（ＴＨＦ）溶液を調製し、イオン源ＦＤ＋、質量範囲６０～１６００のもと、ＦＤ－ＭＳを測定した。
使用機器：日本電子社製 ＪＭＳ－Ｔ２００ＧＣ <FD-MS (field desorption mass spectrometry)>
A 0.2% tetrahydrofuran (THF) solution of the sample was prepared, and FD-MS was measured using an ion source FD+ in a mass range of 60 to 1600.
Equipment used: JMS-T200GC manufactured by JEOL Ltd.
試料の０．２％テトラヒドロフラン（ＴＨＦ）溶液を調製し、イオン源ＦＤ＋、質量範囲６０～１６００のもと、ＦＤ－ＭＳを測定した。
使用機器：日本電子社製 ＪＭＳ－Ｔ２００ＧＣ <FD-MS (field desorption mass spectrometry)>
A 0.2% tetrahydrofuran (THF) solution of the sample was prepared, and FD-MS was measured using an ion source FD+ in a mass range of 60 to 1600.
Equipment used: JMS-T200GC manufactured by JEOL Ltd.
＜ＧＰＣ（ゲル浸透クロマトグラフィ）＞
試料の１％ＴＨＦ溶液を調製し、ＧＰＣ測定を行った。
使用機器：東ソー社製 ＨＬＣ８３２０ＧＰＣ
カラム：ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ＋Ｇ２０００ＨＸＬ＋Ｇ２０００ＨＸＬ <GPC (gel permeation chromatography)>
A 1% THF solution of the sample was prepared and GPC measurement was performed.
Equipment used: Tosoh Corporation HLC8320GPC
Column: TSKgel G3000HXL+G2000HXL+G2000HXL
試料の１％ＴＨＦ溶液を調製し、ＧＰＣ測定を行った。
使用機器：東ソー社製 ＨＬＣ８３２０ＧＰＣ
カラム：ＴＳＫｇｅｌ Ｇ３０００ＨＸＬ＋Ｇ２０００ＨＸＬ＋Ｇ２０００ＨＸＬ <GPC (gel permeation chromatography)>
A 1% THF solution of the sample was prepared and GPC measurement was performed.
Equipment used: Tosoh Corporation HLC8320GPC
Column: TSKgel G3000HXL+G2000HXL+G2000HXL
＜屈折率＞
試料について３種の濃度のＮ－メチル－２－ピロリドン溶液を調製し、各溶液について屈折率計にて、２５．０℃におけるＤ線（波長５８９ｎｍ）の屈折率を測定した。これら３種の濃度を横軸に、それぞれの屈折率を縦軸にプロットし、最小二乗法における近似曲線から、濃度１００％における屈折率を算出し、その値を屈折率とした。
使用機器：京都電子社製 屈折率計ＤＡ－６４５ <Refractive index>
N-methyl-2-pyrrolidone solutions with three different concentrations were prepared for the samples, and the refractive index of each solution at 25.0° C. for the D line (wavelength 589 nm) was measured using a refractometer. The concentrations of these three types were plotted on the horizontal axis and the respective refractive indices were plotted on the vertical axis, and the refractive index at a concentration of 100% was calculated from the approximate curve using the least squares method, and the value was taken as the refractive index.
Equipment used: Refractometer DA-645 manufactured by Kyoto Denshi Co., Ltd.
試料について３種の濃度のＮ－メチル－２－ピロリドン溶液を調製し、各溶液について屈折率計にて、２５．０℃におけるＤ線（波長５８９ｎｍ）の屈折率を測定した。これら３種の濃度を横軸に、それぞれの屈折率を縦軸にプロットし、最小二乗法における近似曲線から、濃度１００％における屈折率を算出し、その値を屈折率とした。
使用機器：京都電子社製 屈折率計ＤＡ－６４５ <Refractive index>
N-methyl-2-pyrrolidone solutions with three different concentrations were prepared for the samples, and the refractive index of each solution at 25.0° C. for the D line (wavelength 589 nm) was measured using a refractometer. The concentrations of these three types were plotted on the horizontal axis and the respective refractive indices were plotted on the vertical axis, and the refractive index at a concentration of 100% was calculated from the approximate curve using the least squares method, and the value was taken as the refractive index.
Equipment used: Refractometer DA-645 manufactured by Kyoto Denshi Co., Ltd.
＜溶解性（１）＞
試料に、化合物の最終的な濃度が８％以上となるようにＮ－メチル－２－ピロリドンを加えた試験管をボルテックスミキサーにて十分に撹拌混合した後、２５℃に調整した水槽にて１０分間放置したときの試料の溶解性を確認した。 <Solubility (1)>
After adding N-methyl-2-pyrrolidone to the sample so that the final concentration of the compound was 8% or more, the test tube was sufficiently stirred and mixed with a vortex mixer, and then the test tube was heated in a water bath adjusted to 25°C for 10 minutes. The solubility of the sample was confirmed when it was left to stand for a minute.
試料に、化合物の最終的な濃度が８％以上となるようにＮ－メチル－２－ピロリドンを加えた試験管をボルテックスミキサーにて十分に撹拌混合した後、２５℃に調整した水槽にて１０分間放置したときの試料の溶解性を確認した。 <Solubility (1)>
After adding N-methyl-2-pyrrolidone to the sample so that the final concentration of the compound was 8% or more, the test tube was sufficiently stirred and mixed with a vortex mixer, and then the test tube was heated in a water bath adjusted to 25°C for 10 minutes. The solubility of the sample was confirmed when it was left to stand for a minute.
＜溶解性（２）＞
屈折率測定用に調製した３種の濃度のＮ－メチル－２－ピロリドン溶液について、２５℃で一日静置した後に目視で、試料の析出の有無を確認した。 <Solubility (2)>
N-methyl-2-pyrrolidone solutions of three concentrations prepared for refractive index measurement were allowed to stand at 25° C. for one day, and then visually checked for the presence or absence of sample precipitation.
屈折率測定用に調製した３種の濃度のＮ－メチル－２－ピロリドン溶液について、２５℃で一日静置した後に目視で、試料の析出の有無を確認した。 <Solubility (2)>
N-methyl-2-pyrrolidone solutions of three concentrations prepared for refractive index measurement were allowed to stand at 25° C. for one day, and then visually checked for the presence or absence of sample precipitation.
〔実施例１〕
撹拌機、温度計、アリーン冷却管を付けた２００ｍＬ四つ口フラスコに、ｏ－クレゾール６４．８６ｇ（０．６０モル）、４－ビフェニルアルデヒド１０．９３ｇ（０．０６モル）、反応溶媒としてイオン交換水１０．９３ｇを仕込み撹拌した。そこにドデシルメルカプタン０．５５９ｇ（０．００２８モル）を添加し、加温により反応溶液を５５℃まで昇温した。５５℃に到達した時点で３５％塩酸１８．４２ｇを８分間かけて添加した。触媒添加により反応溶液の色相は淡黄色から淡紅色に変化した。その後、内温５５℃を保持したまま６時間撹拌を続けた後、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液２３．６０ｇを添加すると反応溶液が徐々に懸濁し、赤紫色の油状粘調物が水に分散した状態となった。ここにイオン交換水１２７．０ｇを添加し撹拌を継続した。この時のフラスコ内の反応溶液のｐＨは７～８となった。この水と油状粘調物を含む反応溶液にシクロペンチルメチルエーテル２８８．３ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。これらを混合し、静置すると、薄く濁った淡橙色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱して減圧濃縮によりエーテル除去を行うことで橙色濃縮物が残留した。この残留物を常温まで放冷し、静置すると、橙色の針状結晶が析出した。この針状結晶を吸引ろ過し、ヌッチェ上の結晶を適量のイソプロピルアルコールとイオン交換水により洗浄すると、淡橙色の残渣となった。これを風乾することにより淡橙色粉末１３．０１ｇを得た。この粉末は、ＧＰＣにより目的化合物と未反応のｏ－クレゾールを主成分とする粉末であることが分かった。目的化合物を単離するために、この粉末にイソプロピルアルコール１３．０ｇとイオン交換水１３．０ｇを加えて加熱溶解し再結晶を行った。これを室温まで放冷し静置すると淡橙色の結晶が析出した。この結晶を吸引ろ過し、ヌッチェ上で適量のイソプロピルアルコールとイオン交換水により洗浄した後、風乾すると、白橙色の粉末８．６３ｇ（理論収量に対する収率３７．９％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１１）に示す化合物であることを確認した。なお、得られた白橙色の粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度が９６．６％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）:δ ２．０６（ｓ，６Ｈ），５．３１（ｓ，１Ｈ），６．７２（ａ ｐａｉｒ ｏｆ ｓ，４Ｈ），６．８３（ｓ，２Ｈ），７．１５（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．３１（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５５（ｄ，Ｊ＝８．３０Ｈｚ，２Ｈ），７．６１（ｄｄ，Ｊ＝７．３Ｈｚ，１．２Ｈｚ，２Ｈ），９．２（ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １６．２，５４．３，１１４．４，１２３．５，１２６．５，１２６．６，１２７．１，１２７.２，１３１．２，１３４．５，１３７．７，１４０．０，１４４．５，１５３．７。 [Example 1]
In a 200 mL four-neck flask equipped with a stirrer, thermometer, and Allene condenser, 64.86 g (0.60 mol) of o-cresol, 10.93 g (0.06 mol) of 4-biphenylaldehyde, and ions as a reaction solvent were placed. 10.93 g of exchanged water was charged and stirred. 0.559 g (0.0028 mol) of dodecyl mercaptan was added thereto, and the reaction solution was heated to 55°C. When the temperature reached 55° C., 18.42 g of 35% hydrochloric acid was added over 8 minutes. Upon addition of the catalyst, the color of the reaction solution changed from pale yellow to pale pink. Thereafter, stirring was continued for 6 hours while maintaining the internal temperature of 55°C, and then the reaction solution was cooled. After cooling to 25° C. or lower, 23.60 g of 30% sodium hydroxide solution was added, and the reaction solution gradually became suspended, forming a reddish-purple oily viscous substance dispersed in water. 127.0 g of ion-exchanged water was added thereto, and stirring was continued. At this time, the pH of the reaction solution in the flask was 7 to 8. 288.3 g of cyclopentyl methyl ether was added to the reaction solution containing water and an oily viscous substance, and the entire amount was transferred to a 1000 mL separating funnel. When these were mixed and allowed to stand, they were separated into a slightly cloudy pale orange ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. The water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, leaving an orange concentrate. When this residue was allowed to cool to room temperature and allowed to stand still, orange needle-shaped crystals were precipitated. The needle-shaped crystals were suction-filtered, and the crystals on the Nutsche were washed with an appropriate amount of isopropyl alcohol and ion-exchanged water, resulting in a pale orange residue. By air drying this, 13.01 g of pale orange powder was obtained. This powder was found by GPC to be a powder whose main component was o-cresol which had not reacted with the target compound. In order to isolate the target compound, 13.0 g of isopropyl alcohol and 13.0 g of ion-exchanged water were added to this powder, and the mixture was heated and dissolved to perform recrystallization. When this was allowed to cool to room temperature and left still, pale orange crystals were precipitated. The crystals were suction-filtered, washed on a Nutsche filter with an appropriate amount of isopropyl alcohol and ion-exchanged water, and then air-dried to obtain 8.63 g of white-orange powder (yield 37.9% based on the theoretical yield).
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (11). The physicochemical properties of the obtained white-orange powder were as follows. Furthermore, the purity was confirmed to be 96.6% by GPC.
Mass spectrum: (m/z) 380.
1 H-NMR: (500 MHz, DMSO-d6): δ 2.06 (s, 6H), 5.31 (s, 1H), 6.72 (a pair of s, 4H), 6.83 (s, 2H), 7.15 (d, J=8.3Hz, 2H), 7.31 (t, J=7.3Hz, 1H), 7.41 (t, J=7.7Hz, 2H), 7. 55 (d, J=8.30Hz, 2H), 7.61 (dd, J=7.3Hz, 1.2Hz, 2H), 9.2 (s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 16.2, 54.3, 114.4, 123.5, 126.5, 126.6, 127.1, 127.2, 131.2, 134.5, 137.7, 140.0, 144.5, 153.7.
撹拌機、温度計、アリーン冷却管を付けた２００ｍＬ四つ口フラスコに、ｏ－クレゾール６４．８６ｇ（０．６０モル）、４－ビフェニルアルデヒド１０．９３ｇ（０．０６モル）、反応溶媒としてイオン交換水１０．９３ｇを仕込み撹拌した。そこにドデシルメルカプタン０．５５９ｇ（０．００２８モル）を添加し、加温により反応溶液を５５℃まで昇温した。５５℃に到達した時点で３５％塩酸１８．４２ｇを８分間かけて添加した。触媒添加により反応溶液の色相は淡黄色から淡紅色に変化した。その後、内温５５℃を保持したまま６時間撹拌を続けた後、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液２３．６０ｇを添加すると反応溶液が徐々に懸濁し、赤紫色の油状粘調物が水に分散した状態となった。ここにイオン交換水１２７．０ｇを添加し撹拌を継続した。この時のフラスコ内の反応溶液のｐＨは７～８となった。この水と油状粘調物を含む反応溶液にシクロペンチルメチルエーテル２８８．３ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。これらを混合し、静置すると、薄く濁った淡橙色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱して減圧濃縮によりエーテル除去を行うことで橙色濃縮物が残留した。この残留物を常温まで放冷し、静置すると、橙色の針状結晶が析出した。この針状結晶を吸引ろ過し、ヌッチェ上の結晶を適量のイソプロピルアルコールとイオン交換水により洗浄すると、淡橙色の残渣となった。これを風乾することにより淡橙色粉末１３．０１ｇを得た。この粉末は、ＧＰＣにより目的化合物と未反応のｏ－クレゾールを主成分とする粉末であることが分かった。目的化合物を単離するために、この粉末にイソプロピルアルコール１３．０ｇとイオン交換水１３．０ｇを加えて加熱溶解し再結晶を行った。これを室温まで放冷し静置すると淡橙色の結晶が析出した。この結晶を吸引ろ過し、ヌッチェ上で適量のイソプロピルアルコールとイオン交換水により洗浄した後、風乾すると、白橙色の粉末８．６３ｇ（理論収量に対する収率３７．９％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１１）に示す化合物であることを確認した。なお、得られた白橙色の粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度が９６．６％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）:δ ２．０６（ｓ，６Ｈ），５．３１（ｓ，１Ｈ），６．７２（ａ ｐａｉｒ ｏｆ ｓ，４Ｈ），６．８３（ｓ，２Ｈ），７．１５（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．３１（ｔ，Ｊ＝７．３Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５５（ｄ，Ｊ＝８．３０Ｈｚ，２Ｈ），７．６１（ｄｄ，Ｊ＝７．３Ｈｚ，１．２Ｈｚ，２Ｈ），９．２（ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １６．２，５４．３，１１４．４，１２３．５，１２６．５，１２６．６，１２７．１，１２７.２，１３１．２，１３４．５，１３７．７，１４０．０，１４４．５，１５３．７。 [Example 1]
In a 200 mL four-neck flask equipped with a stirrer, thermometer, and Allene condenser, 64.86 g (0.60 mol) of o-cresol, 10.93 g (0.06 mol) of 4-biphenylaldehyde, and ions as a reaction solvent were placed. 10.93 g of exchanged water was charged and stirred. 0.559 g (0.0028 mol) of dodecyl mercaptan was added thereto, and the reaction solution was heated to 55°C. When the temperature reached 55° C., 18.42 g of 35% hydrochloric acid was added over 8 minutes. Upon addition of the catalyst, the color of the reaction solution changed from pale yellow to pale pink. Thereafter, stirring was continued for 6 hours while maintaining the internal temperature of 55°C, and then the reaction solution was cooled. After cooling to 25° C. or lower, 23.60 g of 30% sodium hydroxide solution was added, and the reaction solution gradually became suspended, forming a reddish-purple oily viscous substance dispersed in water. 127.0 g of ion-exchanged water was added thereto, and stirring was continued. At this time, the pH of the reaction solution in the flask was 7 to 8. 288.3 g of cyclopentyl methyl ether was added to the reaction solution containing water and an oily viscous substance, and the entire amount was transferred to a 1000 mL separating funnel. When these were mixed and allowed to stand, they were separated into a slightly cloudy pale orange ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. The water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, leaving an orange concentrate. When this residue was allowed to cool to room temperature and allowed to stand still, orange needle-shaped crystals were precipitated. The needle-shaped crystals were suction-filtered, and the crystals on the Nutsche were washed with an appropriate amount of isopropyl alcohol and ion-exchanged water, resulting in a pale orange residue. By air drying this, 13.01 g of pale orange powder was obtained. This powder was found by GPC to be a powder whose main component was o-cresol which had not reacted with the target compound. In order to isolate the target compound, 13.0 g of isopropyl alcohol and 13.0 g of ion-exchanged water were added to this powder, and the mixture was heated and dissolved to perform recrystallization. When this was allowed to cool to room temperature and left still, pale orange crystals were precipitated. The crystals were suction-filtered, washed on a Nutsche filter with an appropriate amount of isopropyl alcohol and ion-exchanged water, and then air-dried to obtain 8.63 g of white-orange powder (yield 37.9% based on the theoretical yield).
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (11). The physicochemical properties of the obtained white-orange powder were as follows. Furthermore, the purity was confirmed to be 96.6% by GPC.
Mass spectrum: (m/z) 380.
1 H-NMR: (500 MHz, DMSO-d6): δ 2.06 (s, 6H), 5.31 (s, 1H), 6.72 (a pair of s, 4H), 6.83 (s, 2H), 7.15 (d, J=8.3Hz, 2H), 7.31 (t, J=7.3Hz, 1H), 7.41 (t, J=7.7Hz, 2H), 7. 55 (d, J=8.30Hz, 2H), 7.61 (dd, J=7.3Hz, 1.2Hz, 2H), 9.2 (s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 16.2, 54.3, 114.4, 123.5, 126.5, 126.6, 127.1, 127.2, 131.2, 134.5, 137.7, 140.0, 144.5, 153.7.
〔実施例２〕
ｏ－クレゾールをｐ－クレゾール６４．８６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液を添加すると、反応溶液は淡紅色から薄茶色に変化し懸濁した。この時のフラスコ内の反応溶液のｐＨは７～８であった。この反応溶液にシクロペンチルメチルエーテル１４４．２ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。ここにイオン交換水１２７．０ｇを加えて混合し、静置すると、薄く濁った淡褐色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱して減圧濃縮によりエーテル除去を行うことで褐色の濃縮物が残留した。この残留物を常温まで放冷し、静置すると、白色の針状結晶が析出した。この針状結晶を吸引ろ過し、ヌッチェ上の結晶を適量のイソプロピルアルコールとイオン交換水により洗浄すると、白色の残渣となった。これを風乾することにより白色粉末８．２３ｇ（理論収量に対する収率３６．１％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１２）に示す化合物であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度９６．４％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．０８（ｓ，６Ｈ），６．０６（ｓ，１Ｈ），６．５５（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），６．７１（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），６．８３（ｄｄ，Ｊ＝８．２Ｈｚ，１．９Ｈｚ，２Ｈ），７．０９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．３１（ｔｔ，Ｊ＝７．３Ｈｚ，１．１Ｈｚ，１Ｈ），７．４２（ｔ，Ｊ＝７．８Ｈｚ，２Ｈ），７．５４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．６３（ｄｄ，Ｊ＝８．５Ｈｚ，１．３Ｈｚ，２Ｈ），９．０７（ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２０．６，４２．４，１１４．９，１２６．３，１２６．５，１２６．６，１２７．２，１２７．４，１２８．９，１２９．７，１２９．９，１３０．１，１３７．４，１４０．１，１４３．６，１５２．６。 [Example 2]
The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of p-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel. 127.0 g of ion-exchanged water was added and mixed, and when the mixture was allowed to stand, the mixture was separated into a slightly cloudy light brown ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. The water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, leaving a brown concentrate. When this residue was allowed to cool to room temperature and allowed to stand still, white needle-like crystals precipitated. The needle-shaped crystals were suction-filtered, and the crystals on the Nutsche were washed with an appropriate amount of isopropyl alcohol and ion-exchanged water, resulting in a white residue. By air-drying this, 8.23 g of white powder (yield 36.1% based on the theoretical yield) was obtained.
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (12). The physicochemical properties of the obtained white powder were as follows. Furthermore, it was confirmed by GPC that the purity was 96.4%.
Mass spectrum: (m/z) 380.
1H -NMR: (500MHz, DMSO-d6): δ 2.08 (s, 6H), 6.06 (s, 1H), 6.55 (d, J = 2.0Hz, 2H), 6.71 (d, J=8.1Hz, 2H), 6.83 (dd, J=8.2Hz, 1.9Hz, 2H), 7.09 (d, J=8.3Hz, 2H), 7.31 ( tt, J = 7.3Hz, 1.1Hz, 1H), 7.42 (t, J = 7.8Hz, 2H), 7.54 (d, J = 8.4Hz, 2H), 7.63 (dd , J=8.5Hz, 1.3Hz, 2H), 9.07(s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 20.6, 42.4, 114.9, 126.3, 126.5, 126.6, 127.2, 127.4, 128.9, 129.7, 129.9, 130.1, 137.4, 140.1, 143.6, 152.6.
ｏ－クレゾールをｐ－クレゾール６４．８６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液を添加すると、反応溶液は淡紅色から薄茶色に変化し懸濁した。この時のフラスコ内の反応溶液のｐＨは７～８であった。この反応溶液にシクロペンチルメチルエーテル１４４．２ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。ここにイオン交換水１２７．０ｇを加えて混合し、静置すると、薄く濁った淡褐色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱して減圧濃縮によりエーテル除去を行うことで褐色の濃縮物が残留した。この残留物を常温まで放冷し、静置すると、白色の針状結晶が析出した。この針状結晶を吸引ろ過し、ヌッチェ上の結晶を適量のイソプロピルアルコールとイオン交換水により洗浄すると、白色の残渣となった。これを風乾することにより白色粉末８．２３ｇ（理論収量に対する収率３６．１％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１２）に示す化合物であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度９６．４％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．０８（ｓ，６Ｈ），６．０６（ｓ，１Ｈ），６．５５（ｄ，Ｊ＝２．０Ｈｚ，２Ｈ），６．７１（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），６．８３（ｄｄ，Ｊ＝８．２Ｈｚ，１．９Ｈｚ，２Ｈ），７．０９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．３１（ｔｔ，Ｊ＝７．３Ｈｚ，１．１Ｈｚ，１Ｈ），７．４２（ｔ，Ｊ＝７．８Ｈｚ，２Ｈ），７．５４（ｄ，Ｊ＝８．４Ｈｚ，２Ｈ），７．６３（ｄｄ，Ｊ＝８．５Ｈｚ，１．３Ｈｚ，２Ｈ），９．０７（ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２０．６，４２．４，１１４．９，１２６．３，１２６．５，１２６．６，１２７．２，１２７．４，１２８．９，１２９．７，１２９．９，１３０．１，１３７．４，１４０．１，１４３．６，１５２．６。 [Example 2]
The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of p-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel. 127.0 g of ion-exchanged water was added and mixed, and when the mixture was allowed to stand, the mixture was separated into a slightly cloudy light brown ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. The water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, leaving a brown concentrate. When this residue was allowed to cool to room temperature and allowed to stand still, white needle-like crystals precipitated. The needle-shaped crystals were suction-filtered, and the crystals on the Nutsche were washed with an appropriate amount of isopropyl alcohol and ion-exchanged water, resulting in a white residue. By air-drying this, 8.23 g of white powder (yield 36.1% based on the theoretical yield) was obtained.
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (12). The physicochemical properties of the obtained white powder were as follows. Furthermore, it was confirmed by GPC that the purity was 96.4%.
Mass spectrum: (m/z) 380.
1H -NMR: (500MHz, DMSO-d6): δ 2.08 (s, 6H), 6.06 (s, 1H), 6.55 (d, J = 2.0Hz, 2H), 6.71 (d, J=8.1Hz, 2H), 6.83 (dd, J=8.2Hz, 1.9Hz, 2H), 7.09 (d, J=8.3Hz, 2H), 7.31 ( tt, J = 7.3Hz, 1.1Hz, 1H), 7.42 (t, J = 7.8Hz, 2H), 7.54 (d, J = 8.4Hz, 2H), 7.63 (dd , J=8.5Hz, 1.3Hz, 2H), 9.07(s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 20.6, 42.4, 114.9, 126.3, 126.5, 126.6, 127.2, 127.4, 128.9, 129.7, 129.9, 130.1, 137.4, 140.1, 143.6, 152.6.
〔比較例１〕
特許第６０１６３０３号公報に記載の実施例１に準じ、以下の手順で、下記式（１３）に示す化合物を合成した。
撹拌機、温度計、アリーン冷却管を付した２００ｍＬ四つ口フラスコに９－フルオレノン１４．４２ｇ（０．０８モル）、レゾルシン８８．０９ｇ（０．８０モル）、反応溶媒としてイオン交換水１４．４２ｇを入れ、撹拌を開始した。ここにドデシルメルカプタン７.４５ｇ（０．０３７モル）を入れ、昇温し、反応溶液が５５℃となった時点で３５％塩酸２４．５８ｇ（０．２４モル）を添加した。これをさらに昇温してゆき、内温１１６℃で還流が開始した。還流開始後４時間の時点でイオン交換水４０．００ｇを注入した。さらにフラスコを冷却し、反応溶液の温度を２５℃とした。この反応溶液を分析ロートに移し、シクロペンチルメチルエーテル１４４．２ｇにて２回抽出し、この２回のエーテル層を一括して分液ロートに移液した。このエーテル層をイオン交換水１７３．０ｇにて２回水洗し、水洗済みエーテル溶液を減圧蒸留によりエーテル除去を行うことでスラリー状物８０．６１ｇを得た。このスラリー状物にイソプロピルアルコール４０．３ｇを加え、還流させることによりスラリーを溶解し、ここにイオン交換水４０．３ｇを入れ、放冷した。冷却により析出した粉末をヌッチェと吸引びんを使用し、吸引ろ過（ろ紙：ＡＤＶＡＮＴＥＣ５Ｃ）により分離し、淡黄色粉末状の粗成物５２．３７ｇを得た。この粗成物１０．００ｇを再度イソプロピルアルコール２２．００ｇに溶解し、一旦還流させ、これを室温まで徐冷した。析出物を吸引ろ過（ろ紙：ＡＤＶＡＮＴＥＣ５Ｃ）により単離し、ヌッチェ上でイオン交換水２２．００ｇにて２回水洗し、これを減圧乾燥させることにより白色粉末状の精製物７．３４ｇを得た。
得られた白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより、下記式（１３）に示す化合物（スピロ［フルオレン９，９’－（２’，７’－ジヒドロキシキサンテン）］）であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより、純度が９７．３％であることを確認した。
マススペクトル：（ｍ／ｚ）３６４。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５．８５（ｓ，１Ｈ），６．１３（ｄｄ，Ｊ＝８．３Ｈｚ，２．４Ｈｚ，２Ｈ），６．３０（ｄ，Ｊ＝２．５Ｈｚ，２Ｈ），６．４９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．０５（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），７．３０（ｔｔ，Ｊ＝７．４Ｈｚ，１．４Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５１（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．６１（ｄｄ，Ｊ＝８．４Ｈｚ，１．２Ｈｚ，２Ｈ），８．９０－９．３０（ａ ｐａｉｒ ｏｆ ｂｒ ｓ，４Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ４１．２，１０２．５，１０５．５，１２１．３，１２６．２，１２６．５，１２９．０，１２９．５，１３０．２，１３７．２，１４０．３，１４５．０，１５５．５，１５６．４。 [Comparative example 1]
According to Example 1 described in Japanese Patent No. 6016303, a compound represented by the following formula (13) was synthesized according to the following procedure.
In a 200 mL four-necked flask equipped with a stirrer, a thermometer, and an Allene condenser, were placed 14.42 g (0.08 mol) of 9-fluorenone, 88.09 g (0.80 mol) of resorcinol, and 14.0 g (0.80 mol) of ion-exchanged water as a reaction solvent. 42g was added and stirring was started. 7.45 g (0.037 mol) of dodecyl mercaptan was added thereto, the temperature was raised, and when the reaction solution reached 55° C., 24.58 g (0.24 mol) of 35% hydrochloric acid was added. The temperature was further increased, and reflux started at an internal temperature of 116°C. Four hours after the start of reflux, 40.00 g of ion-exchanged water was injected. The flask was further cooled to bring the temperature of the reaction solution to 25°C. This reaction solution was transferred to an analytical funnel and extracted twice with 144.2 g of cyclopentyl methyl ether, and the two ether layers were transferred all at once to a separating funnel. This ether layer was washed twice with 173.0 g of ion-exchanged water, and the washed ether solution was subjected to vacuum distillation to remove ether, thereby obtaining 80.61 g of a slurry. 40.3 g of isopropyl alcohol was added to this slurry and refluxed to dissolve the slurry. 40.3 g of ion-exchanged water was added thereto and allowed to cool. The powder precipitated by cooling was separated by suction filtration (filter paper: ADVANTEC5C) using a nutsche and a suction bottle to obtain 52.37 g of a pale yellow powdery crude product. 10.00 g of this crude product was again dissolved in 22.00 g of isopropyl alcohol, once refluxed, and then slowly cooled to room temperature. The precipitate was isolated by suction filtration (filter paper: ADVANTEC5C), washed twice with 22.00 g of ion-exchanged water on a Nutsche filter, and dried under reduced pressure to obtain 7.34 g of a white powdery purified product.
The obtained white powder was analyzed by 1 H-NMR, 13 C-NMR, and FD-MS to detect a compound represented by the following formula (13) (spiro[fluorene 9,9'-(2',7'-dihydroxyxanthene)]). It was confirmed that The physicochemical properties of the obtained white powder were as follows. Furthermore, it was confirmed by GPC that the purity was 97.3%.
Mass spectrum: (m/z)364.
1H -NMR: (500MHz, DMSO-d 6 ): δ 5.85 (s, 1H), 6.13 (dd, J = 8.3Hz, 2.4Hz, 2H), 6.30 (d, J =2.5Hz, 2H), 6.49 (d, J = 8.3Hz, 2H), 7.05 (d, J = 8.1Hz, 2H), 7.30 (tt, J = 7.4Hz, 1.4Hz, 1H), 7.41 (t, J = 7.7Hz, 2H), 7.51 (d, J = 8.3Hz, 2H), 7.61 (dd, J = 8.4Hz, 1 .2Hz, 2H), 8.90-9.30 (a pair of br s, 4H).
13C -NMR: (500MHz, DMSO-d 6 ): δ 41.2, 102.5, 105.5, 121.3, 126.2, 126.5, 129.0, 129.5, 130.2 , 137.2, 140.3, 145.0, 155.5, 156.4.
特許第６０１６３０３号公報に記載の実施例１に準じ、以下の手順で、下記式（１３）に示す化合物を合成した。
撹拌機、温度計、アリーン冷却管を付した２００ｍＬ四つ口フラスコに９－フルオレノン１４．４２ｇ（０．０８モル）、レゾルシン８８．０９ｇ（０．８０モル）、反応溶媒としてイオン交換水１４．４２ｇを入れ、撹拌を開始した。ここにドデシルメルカプタン７.４５ｇ（０．０３７モル）を入れ、昇温し、反応溶液が５５℃となった時点で３５％塩酸２４．５８ｇ（０．２４モル）を添加した。これをさらに昇温してゆき、内温１１６℃で還流が開始した。還流開始後４時間の時点でイオン交換水４０．００ｇを注入した。さらにフラスコを冷却し、反応溶液の温度を２５℃とした。この反応溶液を分析ロートに移し、シクロペンチルメチルエーテル１４４．２ｇにて２回抽出し、この２回のエーテル層を一括して分液ロートに移液した。このエーテル層をイオン交換水１７３．０ｇにて２回水洗し、水洗済みエーテル溶液を減圧蒸留によりエーテル除去を行うことでスラリー状物８０．６１ｇを得た。このスラリー状物にイソプロピルアルコール４０．３ｇを加え、還流させることによりスラリーを溶解し、ここにイオン交換水４０．３ｇを入れ、放冷した。冷却により析出した粉末をヌッチェと吸引びんを使用し、吸引ろ過（ろ紙：ＡＤＶＡＮＴＥＣ５Ｃ）により分離し、淡黄色粉末状の粗成物５２．３７ｇを得た。この粗成物１０．００ｇを再度イソプロピルアルコール２２．００ｇに溶解し、一旦還流させ、これを室温まで徐冷した。析出物を吸引ろ過（ろ紙：ＡＤＶＡＮＴＥＣ５Ｃ）により単離し、ヌッチェ上でイオン交換水２２．００ｇにて２回水洗し、これを減圧乾燥させることにより白色粉末状の精製物７．３４ｇを得た。
得られた白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより、下記式（１３）に示す化合物（スピロ［フルオレン９，９’－（２’，７’－ジヒドロキシキサンテン）］）であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより、純度が９７．３％であることを確認した。
マススペクトル：（ｍ／ｚ）３６４。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５．８５（ｓ，１Ｈ），６．１３（ｄｄ，Ｊ＝８．３Ｈｚ，２．４Ｈｚ，２Ｈ），６．３０（ｄ，Ｊ＝２．５Ｈｚ，２Ｈ），６．４９（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．０５（ｄ，Ｊ＝８．１Ｈｚ，２Ｈ），７．３０（ｔｔ，Ｊ＝７．４Ｈｚ，１．４Ｈｚ，１Ｈ），７．４１（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５１（ｄ，Ｊ＝８．３Ｈｚ，２Ｈ），７．６１（ｄｄ，Ｊ＝８．４Ｈｚ，１．２Ｈｚ，２Ｈ），８．９０－９．３０（ａ ｐａｉｒ ｏｆ ｂｒ ｓ，４Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ４１．２，１０２．５，１０５．５，１２１．３，１２６．２，１２６．５，１２９．０，１２９．５，１３０．２，１３７．２，１４０．３，１４５．０，１５５．５，１５６．４。 [Comparative example 1]
According to Example 1 described in Japanese Patent No. 6016303, a compound represented by the following formula (13) was synthesized according to the following procedure.
In a 200 mL four-necked flask equipped with a stirrer, a thermometer, and an Allene condenser, were placed 14.42 g (0.08 mol) of 9-fluorenone, 88.09 g (0.80 mol) of resorcinol, and 14.0 g (0.80 mol) of ion-exchanged water as a reaction solvent. 42g was added and stirring was started. 7.45 g (0.037 mol) of dodecyl mercaptan was added thereto, the temperature was raised, and when the reaction solution reached 55° C., 24.58 g (0.24 mol) of 35% hydrochloric acid was added. The temperature was further increased, and reflux started at an internal temperature of 116°C. Four hours after the start of reflux, 40.00 g of ion-exchanged water was injected. The flask was further cooled to bring the temperature of the reaction solution to 25°C. This reaction solution was transferred to an analytical funnel and extracted twice with 144.2 g of cyclopentyl methyl ether, and the two ether layers were transferred all at once to a separating funnel. This ether layer was washed twice with 173.0 g of ion-exchanged water, and the washed ether solution was subjected to vacuum distillation to remove ether, thereby obtaining 80.61 g of a slurry. 40.3 g of isopropyl alcohol was added to this slurry and refluxed to dissolve the slurry. 40.3 g of ion-exchanged water was added thereto and allowed to cool. The powder precipitated by cooling was separated by suction filtration (filter paper: ADVANTEC5C) using a nutsche and a suction bottle to obtain 52.37 g of a pale yellow powdery crude product. 10.00 g of this crude product was again dissolved in 22.00 g of isopropyl alcohol, once refluxed, and then slowly cooled to room temperature. The precipitate was isolated by suction filtration (filter paper: ADVANTEC5C), washed twice with 22.00 g of ion-exchanged water on a Nutsche filter, and dried under reduced pressure to obtain 7.34 g of a white powdery purified product.
The obtained white powder was analyzed by 1 H-NMR, 13 C-NMR, and FD-MS to detect a compound represented by the following formula (13) (spiro[fluorene 9,9'-(2',7'-dihydroxyxanthene)]). It was confirmed that The physicochemical properties of the obtained white powder were as follows. Furthermore, it was confirmed by GPC that the purity was 97.3%.
Mass spectrum: (m/z)364.
1H -NMR: (500MHz, DMSO-d 6 ): δ 5.85 (s, 1H), 6.13 (dd, J = 8.3Hz, 2.4Hz, 2H), 6.30 (d, J =2.5Hz, 2H), 6.49 (d, J = 8.3Hz, 2H), 7.05 (d, J = 8.1Hz, 2H), 7.30 (tt, J = 7.4Hz, 1.4Hz, 1H), 7.41 (t, J = 7.7Hz, 2H), 7.51 (d, J = 8.3Hz, 2H), 7.61 (dd, J = 8.4Hz, 1 .2Hz, 2H), 8.90-9.30 (a pair of br s, 4H).
13C -NMR: (500MHz, DMSO-d 6 ): δ 41.2, 102.5, 105.5, 121.3, 126.2, 126.5, 129.0, 129.5, 130.2 , 137.2, 140.3, 145.0, 155.5, 156.4.
〔比較例２〕
比較例２の化合物として、下記式（１４）に示す市販のビスフェノールＡ（三井化学株式会社製）を用意した。 [Comparative example 2]
As a compound of Comparative Example 2, commercially available bisphenol A (manufactured by Mitsui Chemicals, Inc.) shown in the following formula (14) was prepared.
比較例２の化合物として、下記式（１４）に示す市販のビスフェノールＡ（三井化学株式会社製）を用意した。 [Comparative example 2]
As a compound of Comparative Example 2, commercially available bisphenol A (manufactured by Mitsui Chemicals, Inc.) shown in the following formula (14) was prepared.
〔実施例３〕
ｏ－クレゾールをｍ－クレゾール６４．８６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液を添加すると、反応溶液は淡紅色から薄茶色に変化し懸濁した。この時のフラスコ内の反応溶液のｐＨは７～８であった。この反応溶液にシクロペンチルメチルエーテル１４４．２ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。ここにイオン交換水１２７．０ｇを加えて混合し、静置すると、薄く濁った淡褐色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱し、減圧濃縮によりエーテルを除去したところ、褐色の濃縮油状物７０．４ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のｍ－クレゾールを含む混合物であった。この残留物を適量のイソプロピルアルコールとイオン交換水により溶解し、減圧下にて常温から１７５℃まで昇温して濃縮を行った後、常温まで冷却したところ、褐色の固形物残渣が得られた。これを風乾し、粗砕することにより白褐色の粉末１９．７０ｇ（理論収量に対する収率８６．４％）を得た。
この白褐色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１５）に示す化合物（異性体あり）であることを確認した。なお、得られた白褐色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度７９．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．０６－２．２０（ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ），５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ），６．４８－７．６４（ｏｖｅｒｌａｐｐｅｄ，１５Ｈ），９．１３－９．２７（ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １９．４，１９．４，２０．８，２１．１，４１．９，４４．６，４７．９，１１２．１，１１２．３，１１２．４，１１５．７，１１５．９，１１７．２，１１７．３，１１９．２，１１９．４，１１９．６，１２６．３，１２６．４，１２６．５，１２６．６，１２７．０，１２７．１，１２７．２，１２７．３，１２８．９，１２９．２，１２９．５，１２９．９，１３２．５，１３２．８，１３６．１，１３６．３，１３７．１，１３７．４，１３７．６，１３７．８，１３８．７，１３９．９，１４０．１，１４０．２，１４３．０，１４３．５，１４４．０，１５４．２，１５４．６，１５５．４，１５５．５，１５７．３。
なお、１Ｈ－ＮＭＲにおいて、「ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ」は、６つのシングレットピークが重なり合っていたことを示す。同様に、「ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ」は、２つのシングレットピークが重なり合っていたことを示す。「５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ）」は、これら３ピークがいずれもシングレットで、３ピーク合わせて１Ｈ相当であったことを示す。また、１３Ｃ－ＮＭＲにおいて、δ １９．４に２本のピークが重なり合っていたため、同じ値を併記した。後述する実施例４においても同様である。 [Example 3]
The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of m-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel. 127.0 g of ion-exchanged water was added and mixed, and when the mixture was allowed to stand, the mixture was separated into a slightly cloudy light brown ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. When the water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, 70.4 g of a brown concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted m-cresol. This residue was dissolved in an appropriate amount of isopropyl alcohol and ion-exchanged water, concentrated under reduced pressure by raising the temperature from room temperature to 175°C, and then cooled to room temperature to obtain a brown solid residue. . This was air-dried and coarsely crushed to obtain 19.70 g of white-brown powder (yield 86.4% based on the theoretical yield).
When this whitish brown powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound (including isomers) shown in the following formula (15). The physicochemical properties of the obtained white-brown powder were as follows. Furthermore, it was confirmed by GPC that the purity was 79.7%.
Mass spectrum: (m/z) 380.
1 H-NMR: (500MHz, DMSO-d6): δ 2.06-2.20 (overlapped s, 6H), 5.53, 5.80 and 6.00 (s, 1H), 6.48-7 .64 (overlapped, 15H), 9.13-9.27 (overlapped s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 19.4, 19.4, 20.8, 21.1, 41.9, 44.6, 47.9, 112.1, 112.3, 112.4, 115.7, 115.9, 117.2, 117.3, 119.2, 119.4, 119.6, 126.3, 126.4, 126.5, 126.6, 127. 0,127.1,127.2,127.3,128.9,129.2,129.5,129.9,132.5,132.8,136.1,136.3,137.1, 137.4, 137.6, 137.8, 138.7, 139.9, 140.1, 140.2, 143.0, 143.5, 144.0, 154.2, 154.6, 155. 4,155.5,157.3.
Note that in 1 H-NMR, "overlapped s, 6H" indicates that six singlet peaks overlapped. Similarly, "overlapped s, 2H" indicates that two singlet peaks were overlapped. "5.53, 5.80 and 6.00 (s, 1H)" indicates that these three peaks were all singlets, and the three peaks combined were equivalent to 1H. In addition, in 13 C-NMR, two peaks at δ 19.4 overlapped, so the same values were written together. The same applies to Example 4, which will be described later.
ｏ－クレゾールをｍ－クレゾール６４．８６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却した。２５℃以下に冷却後、３０％水酸化ナトリウム溶液を添加すると、反応溶液は淡紅色から薄茶色に変化し懸濁した。この時のフラスコ内の反応溶液のｐＨは７～８であった。この反応溶液にシクロペンチルメチルエーテル１４４．２ｇを加えて、全量を１０００ｍＬ分液ロートへ移液した。ここにイオン交換水１２７．０ｇを加えて混合し、静置すると、薄く濁った淡褐色のエーテル相と無色透明の水相に分離した。水相を除去した後、この分液ロートにてエーテル相にイオン交換水２４６．０ｇを添加して水洗を行い、これを３回繰り返した。水洗済みエーテル溶液を５００ｍＬ三角フラスコにて加熱し、減圧濃縮によりエーテルを除去したところ、褐色の濃縮油状物７０．４ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のｍ－クレゾールを含む混合物であった。この残留物を適量のイソプロピルアルコールとイオン交換水により溶解し、減圧下にて常温から１７５℃まで昇温して濃縮を行った後、常温まで冷却したところ、褐色の固形物残渣が得られた。これを風乾し、粗砕することにより白褐色の粉末１９．７０ｇ（理論収量に対する収率８６．４％）を得た。
この白褐色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１５）に示す化合物（異性体あり）であることを確認した。なお、得られた白褐色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度７９．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．０６－２．２０（ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ），５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ），６．４８－７．６４（ｏｖｅｒｌａｐｐｅｄ，１５Ｈ），９．１３－９．２７（ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １９．４，１９．４，２０．８，２１．１，４１．９，４４．６，４７．９，１１２．１，１１２．３，１１２．４，１１５．７，１１５．９，１１７．２，１１７．３，１１９．２，１１９．４，１１９．６，１２６．３，１２６．４，１２６．５，１２６．６，１２７．０，１２７．１，１２７．２，１２７．３，１２８．９，１２９．２，１２９．５，１２９．９，１３２．５，１３２．８，１３６．１，１３６．３，１３７．１，１３７．４，１３７．６，１３７．８，１３８．７，１３９．９，１４０．１，１４０．２，１４３．０，１４３．５，１４４．０，１５４．２，１５４．６，１５５．４，１５５．５，１５７．３。
なお、１Ｈ－ＮＭＲにおいて、「ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ」は、６つのシングレットピークが重なり合っていたことを示す。同様に、「ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ」は、２つのシングレットピークが重なり合っていたことを示す。「５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ）」は、これら３ピークがいずれもシングレットで、３ピーク合わせて１Ｈ相当であったことを示す。また、１３Ｃ－ＮＭＲにおいて、δ １９．４に２本のピークが重なり合っていたため、同じ値を併記した。後述する実施例４においても同様である。 [Example 3]
The reaction was carried out in the same manner as in Example 1 except that 64.86 g (0.60 mol) of m-cresol was used instead of o-cresol, and the reaction solution was cooled. After cooling to 25° C. or lower, 30% sodium hydroxide solution was added, and the reaction solution changed from pale pink to light brown and became suspended. At this time, the pH of the reaction solution in the flask was 7 to 8. 144.2 g of cyclopentyl methyl ether was added to this reaction solution, and the entire amount was transferred to a 1000 mL separating funnel. 127.0 g of ion-exchanged water was added and mixed, and when the mixture was allowed to stand, the mixture was separated into a slightly cloudy light brown ether phase and a colorless and transparent aqueous phase. After removing the aqueous phase, 246.0 g of ion-exchanged water was added to the ether phase in this separatory funnel to perform water washing, and this was repeated three times. When the water-washed ether solution was heated in a 500 mL Erlenmeyer flask and the ether was removed by vacuum concentration, 70.4 g of a brown concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted m-cresol. This residue was dissolved in an appropriate amount of isopropyl alcohol and ion-exchanged water, concentrated under reduced pressure by raising the temperature from room temperature to 175°C, and then cooled to room temperature to obtain a brown solid residue. . This was air-dried and coarsely crushed to obtain 19.70 g of white-brown powder (yield 86.4% based on the theoretical yield).
When this whitish brown powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound (including isomers) shown in the following formula (15). The physicochemical properties of the obtained white-brown powder were as follows. Furthermore, it was confirmed by GPC that the purity was 79.7%.
Mass spectrum: (m/z) 380.
1 H-NMR: (500MHz, DMSO-d6): δ 2.06-2.20 (overlapped s, 6H), 5.53, 5.80 and 6.00 (s, 1H), 6.48-7 .64 (overlapped, 15H), 9.13-9.27 (overlapped s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 19.4, 19.4, 20.8, 21.1, 41.9, 44.6, 47.9, 112.1, 112.3, 112.4, 115.7, 115.9, 117.2, 117.3, 119.2, 119.4, 119.6, 126.3, 126.4, 126.5, 126.6, 127. 0,127.1,127.2,127.3,128.9,129.2,129.5,129.9,132.5,132.8,136.1,136.3,137.1, 137.4, 137.6, 137.8, 138.7, 139.9, 140.1, 140.2, 143.0, 143.5, 144.0, 154.2, 154.6, 155. 4,155.5,157.3.
Note that in 1 H-NMR, "overlapped s, 6H" indicates that six singlet peaks overlapped. Similarly, "overlapped s, 2H" indicates that two singlet peaks were overlapped. "5.53, 5.80 and 6.00 (s, 1H)" indicates that these three peaks were all singlets, and the three peaks combined were equivalent to 1H. In addition, in 13 C-NMR, two peaks at δ 19.4 overlapped, so the same values were written together. The same applies to Example 4, which will be described later.
〔実施例４〕
ｍ－クレゾールをＭＰ－クレゾール（ｍ－クレゾールとｐ－クレゾールとの混合物、住友化学社製「Ｍ－３０１」）６４．８６ｇ（０．６０モル）とした以外は実施例３と同様にして反応を行い、反応溶液を冷却後、３０％水酸化ナトリウム溶液による中和、シクロペンチルメチルエーテルによる抽出、更に水洗を行った。この水洗済みエーテル溶液について減圧濃縮によりエーテルを除去したところ、褐色の濃縮油状物７７．０ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のＭＰ－クレゾールを含む混合物であった。この残留物を適量のイソプロピルアルコールとイオン交換水により溶解し、減圧下にて常温から１７５℃まで昇温して濃縮を行った後、常温まで冷却したところ、褐色の固形物残渣が得られた。これを風乾し、粗砕することにより白褐色の粉末１８．８０ｇ（理論収量に対する収率８２．５％）を得た。
この白褐色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、前記式（１２）に示す化合物と、前記式（１５）に示す化合物（異性体あり）と、下記式（１６）に示す化合物（異性体あり）との混合物であることを確認した。なお、得られた白褐色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度７９．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．００－２．２０（ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ），５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ），６．４８－７．６４（ｏｖｅｒｌａｐｐｅｄ，１５Ｈ），９．００－９．２７（ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １９．４，１９．４，２０．１，２０．８，２１．１，４１．９，４４．６，４７．９，１１２．１，１１２．３，１１２．４，１１５．１，１１５．７，１１５．９，１１７．２，１１７．３，１１９．２，１１９．４，１１９．６，１２６．１，１２６．３，１２６．４，１２６．５，１２６．６，１２７．２，１２７．２，１２７．３，１２８．８，１２８．９，１２９．２，１２９．５，１２９．７，１２９．９，１３２．５，１３２．８，１３６．１，１３６．３，１３７．１，１３７．４，１３７．６，１３７．８，１３８．７，１３９．９，１４０．０，１４０．１，１４０．２，１４３．０，１４３．５，１４４．０，１５４．５，１５４．６，１５５．０，１５５．４，１５５．５，１５７．３。 [Example 4]
The reaction was carried out in the same manner as in Example 3, except that m-cresol was replaced with 64.86 g (0.60 mol) of MP-cresol (a mixture of m-cresol and p-cresol, "M-301" manufactured by Sumitomo Chemical Co., Ltd.). After cooling the reaction solution, it was neutralized with a 30% sodium hydroxide solution, extracted with cyclopentyl methyl ether, and washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 77.0 g of a brown concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted MP-cresol. This residue was dissolved in an appropriate amount of isopropyl alcohol and ion-exchanged water, concentrated under reduced pressure by raising the temperature from room temperature to 175°C, and then cooled to room temperature to obtain a brown solid residue. . This was air-dried and coarsely crushed to obtain 18.80 g of a whitish brown powder (yield: 82.5% based on the theoretical yield).
When this whitish brown powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was found that the compound represented by the above formula (12), the compound shown by the above formula (15) (with isomers), and the following formula It was confirmed that it was a mixture with the compound shown in (16) (including isomers). The physicochemical properties of the obtained white-brown powder were as follows. Furthermore, it was confirmed by GPC that the purity was 79.7%.
Mass spectrum: (m/z) 380.
1 H-NMR: (500MHz, DMSO-d6): δ 2.00-2.20 (overlapped s, 6H), 5.53, 5.80 and 6.00 (s, 1H), 6.48-7 .64 (overlapped, 15H), 9.00-9.27 (overlapped s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 19.4, 19.4, 20.1, 20.8, 21.1, 41.9, 44.6, 47.9, 112.1, 112.3, 112.4, 115.1, 115.7, 115.9, 117.2, 117.3, 119.2, 119.4, 119.6, 126.1, 126.3, 126. 4,126.5,126.6,127.2,127.2,127.3,128.8,128.9,129.2,129.5,129.7,129.9,132.5, 132.8, 136.1, 136.3, 137.1, 137.4, 137.6, 137.8, 138.7, 139.9, 140.0, 140.1, 140.2, 143. 0,143.5,144.0,154.5,154.6,155.0,155.4,155.5,157.3.
ｍ－クレゾールをＭＰ－クレゾール（ｍ－クレゾールとｐ－クレゾールとの混合物、住友化学社製「Ｍ－３０１」）６４．８６ｇ（０．６０モル）とした以外は実施例３と同様にして反応を行い、反応溶液を冷却後、３０％水酸化ナトリウム溶液による中和、シクロペンチルメチルエーテルによる抽出、更に水洗を行った。この水洗済みエーテル溶液について減圧濃縮によりエーテルを除去したところ、褐色の濃縮油状物７７．０ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のＭＰ－クレゾールを含む混合物であった。この残留物を適量のイソプロピルアルコールとイオン交換水により溶解し、減圧下にて常温から１７５℃まで昇温して濃縮を行った後、常温まで冷却したところ、褐色の固形物残渣が得られた。これを風乾し、粗砕することにより白褐色の粉末１８．８０ｇ（理論収量に対する収率８２．５％）を得た。
この白褐色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、前記式（１２）に示す化合物と、前記式（１５）に示す化合物（異性体あり）と、下記式（１６）に示す化合物（異性体あり）との混合物であることを確認した。なお、得られた白褐色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度７９．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３８０。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ２．００－２．２０（ｏｖｅｒｌａｐｐｅｄ ｓ，６Ｈ），５．５３，５．８０ ａｎｄ ６．００（ｓ，１Ｈ），６．４８－７．６４（ｏｖｅｒｌａｐｐｅｄ，１５Ｈ），９．００－９．２７（ｏｖｅｒｌａｐｐｅｄ ｓ，２Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ １９．４，１９．４，２０．１，２０．８，２１．１，４１．９，４４．６，４７．９，１１２．１，１１２．３，１１２．４，１１５．１，１１５．７，１１５．９，１１７．２，１１７．３，１１９．２，１１９．４，１１９．６，１２６．１，１２６．３，１２６．４，１２６．５，１２６．６，１２７．２，１２７．２，１２７．３，１２８．８，１２８．９，１２９．２，１２９．５，１２９．７，１２９．９，１３２．５，１３２．８，１３６．１，１３６．３，１３７．１，１３７．４，１３７．６，１３７．８，１３８．７，１３９．９，１４０．０，１４０．１，１４０．２，１４３．０，１４３．５，１４４．０，１５４．５，１５４．６，１５５．０，１５５．４，１５５．５，１５７．３。 [Example 4]
The reaction was carried out in the same manner as in Example 3, except that m-cresol was replaced with 64.86 g (0.60 mol) of MP-cresol (a mixture of m-cresol and p-cresol, "M-301" manufactured by Sumitomo Chemical Co., Ltd.). After cooling the reaction solution, it was neutralized with a 30% sodium hydroxide solution, extracted with cyclopentyl methyl ether, and washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 77.0 g of a brown concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted MP-cresol. This residue was dissolved in an appropriate amount of isopropyl alcohol and ion-exchanged water, concentrated under reduced pressure by raising the temperature from room temperature to 175°C, and then cooled to room temperature to obtain a brown solid residue. . This was air-dried and coarsely crushed to obtain 18.80 g of a whitish brown powder (yield: 82.5% based on the theoretical yield).
When this whitish brown powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was found that the compound represented by the above formula (12), the compound shown by the above formula (15) (with isomers), and the following formula It was confirmed that it was a mixture with the compound shown in (16) (including isomers). The physicochemical properties of the obtained white-brown powder were as follows. Furthermore, it was confirmed by GPC that the purity was 79.7%.
Mass spectrum: (m/z) 380.
1 H-NMR: (500MHz, DMSO-d6): δ 2.00-2.20 (overlapped s, 6H), 5.53, 5.80 and 6.00 (s, 1H), 6.48-7 .64 (overlapped, 15H), 9.00-9.27 (overlapped s, 2H).
13C -NMR: (500MHz, DMSO-d6): δ 19.4, 19.4, 20.1, 20.8, 21.1, 41.9, 44.6, 47.9, 112.1, 112.3, 112.4, 115.1, 115.7, 115.9, 117.2, 117.3, 119.2, 119.4, 119.6, 126.1, 126.3, 126. 4,126.5,126.6,127.2,127.2,127.3,128.8,128.9,129.2,129.5,129.7,129.9,132.5, 132.8, 136.1, 136.3, 137.1, 137.4, 137.6, 137.8, 138.7, 139.9, 140.0, 140.1, 140.2, 143. 0,143.5,144.0,154.5,154.6,155.0,155.4,155.5,157.3.
〔実施例５〕
ｏ－クレゾールをフェノール５６．４６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却後、３０％水酸化ナトリウム溶液による中和、シクロペンチルメチルエーテルによる抽出、更に水洗を行った。この水洗済みエーテル溶液について減圧濃縮によりエーテルを除去したところ、赤橙色の濃縮油状物３２．６ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のフェノールを含む混合物であった。この残留物を、イソプロピルアルコール３．２ｇとイオン交換水３．２ｇを加えて加熱溶解し、再結晶を行った。これを室温まで放冷し静置すると白橙色の結晶が析出し、この結晶を吸引ろ過した。この結晶には未反応のフェノールがまだ含まれていたため、更にこの結晶をイソプロピルアルコールとイオン交換水に加熱溶解し、再結晶を行った結果、白色の結晶が析出した。この結晶を吸引ろ過し、ヌッチェ上で適量のイソプロピルアルコールとイオン交換水により洗浄した後、風乾すると、白色の粉末６．１５ｇ（理論収量に対する収率２９．１％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１７）に示す化合物であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度が９５．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３５２。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５．３９（ｓ，１Ｈ），６．７１（ｄｔ，Ｊ＝８．７Ｈｚ，２．５Ｈｚ，４Ｈ），６．９２（ｄｔ，Ｊ＝８．６Ｈｚ，２．４Ｈｚ，４Ｈ），７．１５（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．３１（ｔｔ，Ｊ＝７．４Ｈｚ，１．４Ｈｚ，１Ｈ），７．４２（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５６（ｄｔ，Ｊ＝８．４Ｈｚ，１．８Ｈｚ，２Ｈ），７．６１（ｄｔ，Ｊ＝７．２Ｈｚ，１．４Ｈｚ，２Ｈ），９．３０（ｓ，１Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５４．１，１１５．１，１２６．５，１２６．６，１２７．３，１２８．９，１２９．５，１２９．９，１３４．６，１３７．８，１４０．０，１４４．４，１５５．６。 [Example 5]
The reaction was carried out in the same manner as in Example 1, except that o-cresol was changed to 56.46 g (0.60 mol) of phenol. After cooling the reaction solution, it was neutralized with 30% sodium hydroxide solution and extracted with cyclopentyl methyl ether. , and further washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 32.6 g of a reddish-orange concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted phenol. This residue was heated and dissolved by adding 3.2 g of isopropyl alcohol and 3.2 g of ion-exchanged water, and recrystallized. When this was allowed to cool to room temperature and left still, white-orange crystals were precipitated, and these crystals were filtered under suction. Since this crystal still contained unreacted phenol, this crystal was further heated and dissolved in isopropyl alcohol and ion-exchanged water to perform recrystallization, resulting in the precipitation of white crystals. The crystals were suction-filtered, washed on a Nutsche filter with an appropriate amount of isopropyl alcohol and ion-exchanged water, and then air-dried to obtain 6.15 g of white powder (yield 29.1% based on the theoretical yield).
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (17). The physicochemical properties of the obtained white powder were as follows. Further, the purity was confirmed to be 95.7% by GPC.
Mass spectrum: (m/z) 352.
1 H-NMR: (500MHz, DMSO-d6): δ 5.39 (s, 1H), 6.71 (dt, J = 8.7Hz, 2.5Hz, 4H), 6.92 (dt, J = 8.6Hz, 2.4Hz, 4H), 7.15 (d, J = 8.2Hz, 2H), 7.31 (tt, J = 7.4Hz, 1.4Hz, 1H), 7.42 (t , J=7.7Hz, 2H), 7.56 (dt, J=8.4Hz, 1.8Hz, 2H), 7.61 (dt, J=7.2Hz, 1.4Hz, 2H), 9. 30 (s, 1H).
13C -NMR: (500MHz, DMSO-d6): δ 54.1, 115.1, 126.5, 126.6, 127.3, 128.9, 129.5, 129.9, 134.6, 137.8, 140.0, 144.4, 155.6.
ｏ－クレゾールをフェノール５６．４６ｇ（０．６０モル）とした以外は実施例１と同様にして反応を行い、反応溶液を冷却後、３０％水酸化ナトリウム溶液による中和、シクロペンチルメチルエーテルによる抽出、更に水洗を行った。この水洗済みエーテル溶液について減圧濃縮によりエーテルを除去したところ、赤橙色の濃縮油状物３２．６ｇが残留した。この残留物はＧＰＣより、目的化合物と未反応のフェノールを含む混合物であった。この残留物を、イソプロピルアルコール３．２ｇとイオン交換水３．２ｇを加えて加熱溶解し、再結晶を行った。これを室温まで放冷し静置すると白橙色の結晶が析出し、この結晶を吸引ろ過した。この結晶には未反応のフェノールがまだ含まれていたため、更にこの結晶をイソプロピルアルコールとイオン交換水に加熱溶解し、再結晶を行った結果、白色の結晶が析出した。この結晶を吸引ろ過し、ヌッチェ上で適量のイソプロピルアルコールとイオン交換水により洗浄した後、風乾すると、白色の粉末６．１５ｇ（理論収量に対する収率２９．１％）を得た。
この白色粉末について１Ｈ－ＮＭＲ、１３Ｃ－ＮＭＲ、ＦＤ－ＭＳにより定性したところ、下記式（１７）に示す化合物であることを確認した。なお、得られた白色粉末の理化学的性質は以下のとおりであった。また、ＧＰＣより純度が９５．７％であることを確認した。
マススペクトル：（ｍ／ｚ）３５２。
１Ｈ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５．３９（ｓ，１Ｈ），６．７１（ｄｔ，Ｊ＝８．７Ｈｚ，２．５Ｈｚ，４Ｈ），６．９２（ｄｔ，Ｊ＝８．６Ｈｚ，２．４Ｈｚ，４Ｈ），７．１５（ｄ，Ｊ＝８．２Ｈｚ，２Ｈ），７．３１（ｔｔ，Ｊ＝７．４Ｈｚ，１．４Ｈｚ，１Ｈ），７．４２（ｔ，Ｊ＝７．７Ｈｚ，２Ｈ），７．５６（ｄｔ，Ｊ＝８．４Ｈｚ，１．８Ｈｚ，２Ｈ），７．６１（ｄｔ，Ｊ＝７．２Ｈｚ，１．４Ｈｚ，２Ｈ），９．３０（ｓ，１Ｈ）。
１３Ｃ－ＮＭＲ：（５００ＭＨｚ，ＤＭＳＯ－ｄ６）：δ ５４．１，１１５．１，１２６．５，１２６．６，１２７．３，１２８．９，１２９．５，１２９．９，１３４．６，１３７．８，１４０．０，１４４．４，１５５．６。 [Example 5]
The reaction was carried out in the same manner as in Example 1, except that o-cresol was changed to 56.46 g (0.60 mol) of phenol. After cooling the reaction solution, it was neutralized with 30% sodium hydroxide solution and extracted with cyclopentyl methyl ether. , and further washed with water. When the ether was removed from this water-washed ether solution by concentration under reduced pressure, 32.6 g of a reddish-orange concentrated oil remained. This residue was determined by GPC to be a mixture containing the target compound and unreacted phenol. This residue was heated and dissolved by adding 3.2 g of isopropyl alcohol and 3.2 g of ion-exchanged water, and recrystallized. When this was allowed to cool to room temperature and left still, white-orange crystals were precipitated, and these crystals were filtered under suction. Since this crystal still contained unreacted phenol, this crystal was further heated and dissolved in isopropyl alcohol and ion-exchanged water to perform recrystallization, resulting in the precipitation of white crystals. The crystals were suction-filtered, washed on a Nutsche filter with an appropriate amount of isopropyl alcohol and ion-exchanged water, and then air-dried to obtain 6.15 g of white powder (yield 29.1% based on the theoretical yield).
When this white powder was qualitatively characterized by 1 H-NMR, 13 C-NMR, and FD-MS, it was confirmed that it was a compound represented by the following formula (17). The physicochemical properties of the obtained white powder were as follows. Further, the purity was confirmed to be 95.7% by GPC.
Mass spectrum: (m/z) 352.
1 H-NMR: (500MHz, DMSO-d6): δ 5.39 (s, 1H), 6.71 (dt, J = 8.7Hz, 2.5Hz, 4H), 6.92 (dt, J = 8.6Hz, 2.4Hz, 4H), 7.15 (d, J = 8.2Hz, 2H), 7.31 (tt, J = 7.4Hz, 1.4Hz, 1H), 7.42 (t , J=7.7Hz, 2H), 7.56 (dt, J=8.4Hz, 1.8Hz, 2H), 7.61 (dt, J=7.2Hz, 1.4Hz, 2H), 9. 30 (s, 1H).
13C -NMR: (500MHz, DMSO-d6): δ 54.1, 115.1, 126.5, 126.6, 127.3, 128.9, 129.5, 129.9, 134.6, 137.8, 140.0, 144.4, 155.6.
表１～２に、実施例１～５および比較例１～２の各例の化合物の屈折率の測定に用いた溶液の濃度と屈折率、それらに基づいて求めた屈折率、溶解性（１）および溶解性（２）の評価結果を示す。
屈折率については、小数点第３位を四捨五入した値を示した。（ ）内に、小数点第４位までの値を併記した。 Tables 1 and 2 show the concentration and refractive index of the solutions used to measure the refractive index of the compounds of Examples 1 and 5 and Comparative Examples 1 and 2, the refractive index determined based on them, and the solubility (1 ) and solubility (2) evaluation results are shown.
The refractive index is a value rounded to the third decimal place. Values to the fourth decimal place are also written in parentheses.
屈折率については、小数点第３位を四捨五入した値を示した。（ ）内に、小数点第４位までの値を併記した。 Tables 1 and 2 show the concentration and refractive index of the solutions used to measure the refractive index of the compounds of Examples 1 and 5 and Comparative Examples 1 and 2, the refractive index determined based on them, and the solubility (1 ) and solubility (2) evaluation results are shown.
The refractive index is a value rounded to the third decimal place. Values to the fourth decimal place are also written in parentheses.
なお、実施例１～５、比較例１～２それぞれの溶解性（１）の評価において設定した「化合物の最終的な濃度」と「溶解可否」の結果は以下のとおりであった。○は溶解可であったことを示し、×は溶解不可であったことを示す。
［実施例１］
濃度９．１３％：○、濃度１６．６０％：○、濃度２３．３６％：○
［実施例２］
濃度８．９８％：○、濃度１６．６６％：○
［比較例１］
濃度７．３０％：○、濃度８．０５％：×
［比較例２］
濃度８．１４％：○、濃度１０．７２％：○
［実施例３］
濃度９．０７％：○、濃度１６．７７％：○
［実施例４］
濃度９．０６％：○、濃度１６．７８％：○
［実施例５］
濃度８．５０％：○、濃度１６．６０％：○ The results of the "final concentration of the compound" and "solubility" set in the evaluation of solubility (1) for Examples 1 to 5 and Comparative Examples 1 to 2 were as follows. ○ indicates that it was soluble, and × indicates that it was not soluble.
[Example 1]
Concentration 9.13%:○, Concentration 16.60%:○, Concentration 23.36%:○
[Example 2]
Concentration 8.98%:○, Concentration 16.66%:○
[Comparative example 1]
Concentration 7.30%: ○, concentration 8.05%: ×
[Comparative example 2]
Concentration 8.14%:○, Concentration 10.72%:○
[Example 3]
Concentration 9.07%: ○, Concentration 16.77%: ○
[Example 4]
Concentration 9.06%:○, Concentration 16.78%:○
[Example 5]
Concentration 8.50%:○, Concentration 16.60%:○
［実施例１］
濃度９．１３％：○、濃度１６．６０％：○、濃度２３．３６％：○
［実施例２］
濃度８．９８％：○、濃度１６．６６％：○
［比較例１］
濃度７．３０％：○、濃度８．０５％：×
［比較例２］
濃度８．１４％：○、濃度１０．７２％：○
［実施例３］
濃度９．０７％：○、濃度１６．７７％：○
［実施例４］
濃度９．０６％：○、濃度１６．７８％：○
［実施例５］
濃度８．５０％：○、濃度１６．６０％：○ The results of the "final concentration of the compound" and "solubility" set in the evaluation of solubility (1) for Examples 1 to 5 and Comparative Examples 1 to 2 were as follows. ○ indicates that it was soluble, and × indicates that it was not soluble.
[Example 1]
Concentration 9.13%:○, Concentration 16.60%:○, Concentration 23.36%:○
[Example 2]
Concentration 8.98%:○, Concentration 16.66%:○
[Comparative example 1]
Concentration 7.30%: ○, concentration 8.05%: ×
[Comparative example 2]
Concentration 8.14%:○, Concentration 10.72%:○
[Example 3]
Concentration 9.07%: ○, Concentration 16.77%: ○
[Example 4]
Concentration 9.06%:○, Concentration 16.78%:○
[Example 5]
Concentration 8.50%:○, Concentration 16.60%:○
比較例１の化合物は、ポリカーボネート樹脂の原料等として一般的な比較例２の化合物に比べ、高屈折率であるものの、溶剤溶解性に劣っていた。
これに対し、実施例１～５の化合物は、比較例２の化合物よりも高屈折率であり、しかも溶剤溶解性に優れていた。 Although the compound of Comparative Example 1 had a higher refractive index than the compound of Comparative Example 2, which is generally used as a raw material for polycarbonate resin, it was inferior in solvent solubility.
On the other hand, the compounds of Examples 1 to 5 had a higher refractive index than the compound of Comparative Example 2, and had excellent solvent solubility.
これに対し、実施例１～５の化合物は、比較例２の化合物よりも高屈折率であり、しかも溶剤溶解性に優れていた。 Although the compound of Comparative Example 1 had a higher refractive index than the compound of Comparative Example 2, which is generally used as a raw material for polycarbonate resin, it was inferior in solvent solubility.
On the other hand, the compounds of Examples 1 to 5 had a higher refractive index than the compound of Comparative Example 2, and had excellent solvent solubility.
本発明によれば、新規な骨格を持つ高屈折率の光学部材およびその製造方法、ならびに新規な骨格を持つ高屈折率の光学部材が得られる光学部材形成材料およびその製造方法を提供できる。
According to the present invention, it is possible to provide a high refractive index optical member having a novel skeleton and a method for manufacturing the same, and an optical member forming material from which a high refractive index optical member having a novel skeleton can be obtained and a manufacturing method for the same.
Claims (13)
- 下記式（ｉ）で表される構造を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 An optical member including a structure represented by the following formula (i).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different. - 下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 An optical member comprising a resin having a structural unit based on a compound represented by the following formula (1).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different. - 前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である請求項２に記載の光学部材。 The optical member according to claim 2, wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
- 前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である請求項２に記載の光学部材。 The optical member according to claim 2, wherein the resin is a polycarbonate resin or a polyester resin.
- 下記式（２）で表される化合物を含む硬化性組成物の硬化物を含む、光学部材。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 An optical member comprising a cured product of a curable composition containing a compound represented by the following formula (2).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different. - 下記式（１）で表される化合物に基づく構成単位を有する樹脂を含む、光学部材形成材料。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 An optical member forming material containing a resin having a structural unit based on a compound represented by the following formula (1).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different. - 前記樹脂が、多価ヒドロキシ化合物をモノマー成分とする樹脂である請求項６に記載の光学部材形成材料。 The optical member forming material according to claim 6, wherein the resin is a resin containing a polyhydric hydroxy compound as a monomer component.
- 前記樹脂が、ポリカーボネート樹脂またはポリエステル樹脂である請求項６に記載の光学部材形成材料。 The optical member forming material according to claim 6, wherein the resin is a polycarbonate resin or a polyester resin.
- 下記式（２）で表される化合物を含む硬化性組成物である、光学部材形成材料。
ａは０～５の整数であり、ｂは０～４の整数であり、
Ｒ２は置換基であり、（ａ＋ｂ）が２以上である場合、（ａ＋ｂ）個のＲ２は同一でも異なっていてもよく、
ｃおよびｄは、それぞれ独立に０～６の整数であり、
Ｒ３は、アルキレン基であり、（ｃ＋ｄ）が２以上である場合、（ｃ＋ｄ）個のＲ３は同一でも異なっていてもよく、
ｅおよびｆは、それぞれ独立に１～５の整数であり、ｇおよびｈは、それぞれ独立に０～４の整数であり、（ｅ＋ｇ）は１～５であり、（ｆ＋ｈ）は１～５であり、
Ｘは、重合性官能基もしくは反応性官能基を含む１価基、または水素原子であり、（ｅ＋ｆ）個のＸは同一でも異なっていてもよく、（ｅ＋ｆ）個のＸのうち少なくとも１個は前記１価基であり、
Ｒ４は、置換基であり、（ｇ＋ｈ）が２以上である場合、（ｇ＋ｈ）個のＲ４は同一でも異なっていてもよい。 An optical member forming material which is a curable composition containing a compound represented by the following formula (2).
a is an integer from 0 to 5, b is an integer from 0 to 4,
R 2 is a substituent, and when (a + b) is 2 or more, (a + b) R 2 may be the same or different,
c and d are each independently an integer of 0 to 6,
R 3 is an alkylene group, and when (c + d) is 2 or more, (c + d) R 3 may be the same or different,
e and f are each independently an integer of 1 to 5, g and h are each independently an integer of 0 to 4, (e+g) is 1 to 5, and (f+h) is 1 to 5. can be,
X is a monovalent group containing a polymerizable functional group or a reactive functional group, or a hydrogen atom, and (e+f) Xs may be the same or different, and at least one of the (e+f) Xs is the monovalent group,
R 4 is a substituent, and when (g+h) is 2 or more, (g+h) R 4 may be the same or different. - 請求項６～８のいずれか１項に記載の光学部材形成材料を製造する方法であって、
モノマー成分の少なくとも一部に前記式（１）で表される化合物を用いて前記樹脂を製造する工程を有する、光学部材形成材料の製造方法。 A method for manufacturing the optical member forming material according to any one of claims 6 to 8, comprising:
A method for producing an optical member forming material, comprising the step of producing the resin using a compound represented by the formula (1) as at least a part of the monomer components. - 請求項９に記載の光学部材形成材料を製造する方法であって、
前記式（２）中のＯＸが全てＯＨである化合物の前記ＯＨの少なくとも一部に、重合性官能基または反応性官能基を含む１価基を付加して前記式（２）で表される化合物を製造する工程を有する、光学部材形成材料の製造方法。 A method for manufacturing the optical member forming material according to claim 9, comprising:
A monovalent group containing a polymerizable functional group or a reactive functional group is added to at least a portion of the OH of a compound in which all OX in the formula (2) are OH, and the compound is represented by the formula (2). A method for producing an optical member forming material, comprising a step of producing a compound. - 請求項６～８のいずれか１項に記載の光学部材形成材料を成形する、光学部材の製造方法。 A method for manufacturing an optical member, comprising molding the optical member forming material according to any one of claims 6 to 8.
- 請求項９に記載の光学部材形成材料を硬化する、光学部材の製造方法。 A method for manufacturing an optical member, which comprises curing the optical member forming material according to claim 9.
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| JP2006160663A (en) * | 2004-12-07 | 2006-06-22 | Honshu Chem Ind Co Ltd | Method for producing 1,1'-bis(2-hydroxynaphthyl) |
| JP2007199653A (en) * | 2005-12-27 | 2007-08-09 | Shin Etsu Chem Co Ltd | Photoresist underlayer film forming material and pattern forming method |
| US20140128494A1 (en) * | 2010-07-07 | 2014-05-08 | California Institute Of Technology | On-demand photoinitiated polymerization |
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| JP2006160663A (en) * | 2004-12-07 | 2006-06-22 | Honshu Chem Ind Co Ltd | Method for producing 1,1'-bis(2-hydroxynaphthyl) |
| JP2007199653A (en) * | 2005-12-27 | 2007-08-09 | Shin Etsu Chem Co Ltd | Photoresist underlayer film forming material and pattern forming method |
| US20140128494A1 (en) * | 2010-07-07 | 2014-05-08 | California Institute Of Technology | On-demand photoinitiated polymerization |
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