WO2023195346A1 - 紫外線吸収剤 - Google Patents

紫外線吸収剤 Download PDF

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Publication number
WO2023195346A1
WO2023195346A1 PCT/JP2023/011390 JP2023011390W WO2023195346A1 WO 2023195346 A1 WO2023195346 A1 WO 2023195346A1 JP 2023011390 W JP2023011390 W JP 2023011390W WO 2023195346 A1 WO2023195346 A1 WO 2023195346A1
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Prior art keywords
group
ultraviolet
resin
ultraviolet absorber
ultraviolet absorbing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2023/011390
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English (en)
French (fr)
Japanese (ja)
Inventor
将吾 菅
善也 大田
渓子 三ノ上
真哉人 光實
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Gas Chemicals Co Ltd
Original Assignee
Osaka Gas Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Osaka Gas Chemicals Co Ltd filed Critical Osaka Gas Chemicals Co Ltd
Priority to JP2024514217A priority Critical patent/JPWO2023195346A1/ja
Priority to EP23784636.5A priority patent/EP4506327A1/en
Priority to CN202380030928.1A priority patent/CN118946648A/zh
Priority to US18/853,401 priority patent/US20250215231A1/en
Priority to KR1020247032416A priority patent/KR20250002172A/ko
Publication of WO2023195346A1 publication Critical patent/WO2023195346A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2203/00—Function characteristic
    • G02F2203/05—Function characteristic wavelength dependent
    • G02F2203/055—Function characteristic wavelength dependent wavelength filtering

Definitions

  • the present invention provides an ultraviolet absorber with excellent ultraviolet absorption in the UV-A and UV-B regions, an ultraviolet absorbing resin, an ultraviolet absorbing coating liquid, an ultraviolet absorbing coated resin sheet, an ultraviolet absorbing coated glass, It relates to ultraviolet absorbing molded bodies, ultraviolet absorbing films, polarizer protective films, polarizing plates, image display devices, transportation equipment, and building material parts.
  • UV-A long wavelength ultraviolet rays
  • UV-B medium wavelength ultraviolet rays
  • UV-C short wavelength ultraviolet rays
  • the wavelength of ultraviolet light that tends to induce deterioration differs depending on the type, but for example, many polymer materials such as polyethylene and polyvinyl chloride are significantly degraded by UV-B, causing discoloration and a decrease in mechanical strength. Since this is known, it is widely practiced to add ultraviolet absorbers that absorb UV-B.
  • UV absorbers that can absorb not only UV-B but also UV-A, especially in fields such as displays, solar cells, and automobiles.
  • conventional organic UV absorbers have low absorption of long-wavelength UV rays, so it was necessary to increase the amount added, but adding too much can cause bleed-out and a decrease in the mechanical strength, heat resistance, and transparency of the resin.
  • UV absorbers which are characterized by their ability to absorb long-wavelength ultraviolet rays, absorb into the visible light range of 400 nm or more, so they are often colored yellow, achieving both ultraviolet absorption performance in the UV-A region and low coloring properties. It was considered difficult to do so.
  • optical films used to improve visibility in display devices such as liquid crystal displays (LCDs) and organic EL displays (OLEDs) are sensitive to ultraviolet rays contained in sunlight as well as ultraviolet rays contained in the light source of display devices. Due to long-term exposure, deterioration such as yellowing progresses over time, resulting in a problem of decreased visibility. Furthermore, with the need for miniaturization of display devices, there is a need for excellent ultraviolet absorbers that can exhibit sufficient ultraviolet absorption performance even when optical films are made thinner.
  • Patent Document 1 discloses a (meth)acrylic film to which a benzotriazole-based ultraviolet absorber is added.
  • benzotriazole-based UV absorbers do not have a sufficient molar absorption coefficient in the UV-A region and must be added at high concentrations, so compositions containing benzotriazole-based UV absorbers may suffer from whitening due to bleed-out. The problem was that it was prone to embrittlement.
  • Patent Document 2 discloses an ultraviolet absorber made of a triazine compound that has strong absorption over a wide range of UV-A regions.
  • triazine-based ultraviolet absorbers which generally absorb ultraviolet rays in a wide wavelength range, also absorb visible rays of 400 nm or more, so they tend to be colored easily.
  • Patent Document 3 discloses a method of combining an ultraviolet absorber having an absorption maximum in a wavelength range of 200 to 300 nm and an ultraviolet absorber having an absorption maximum in a wavelength range of 320 to 400 nm. This has made it possible to achieve both ultraviolet absorption performance at a wavelength of 380 nm and low coloration, but in order to further improve ultraviolet absorption performance and reduce coloration, a new type of ultraviolet light that only absorbs ultraviolet light at a specific wavelength must be developed. It is assumed that an absorbent will be required.
  • Patent Document 4 discloses an ultraviolet absorbent composition characterized by having a maximum absorption wavelength of 350 nm or more and 400 nm or less, a half-width of 55 nm or less, and a molar extinction coefficient of 20,000 or more at the maximum absorption wavelength.
  • a maximum absorption wavelength 350 nm or more and 400 nm or less
  • a half-width 55 nm or less
  • a molar extinction coefficient of 20,000 or more at the maximum absorption wavelength As a result, it has become possible to provide a material that absorbs only ultraviolet rays of a specific wavelength and has little coloration.However, all of the compositions disclosed in the present invention have complex synthesis methods and high costs, so they cannot be used for general purpose use. The problem was that it was difficult to use.
  • Patent Document 5 discloses a resin composition in which a benzotriazole derivative compound is homopolymerized
  • Patent Document 6 discloses a compound in which a reactive functional group is added to the terminal of a compound having a triazine skeleton.
  • the functional groups that contribute to ultraviolet absorption are conventionally known functional groups such as benzotriazole and triazine, so as shown above, the molar absorption coefficient in the UV-A region is insufficient and coloration is a problem. The problem was that it was easy to do.
  • Japanese Patent Application Publication No. 2019-167411 Japanese Patent Application Publication No. 2016-102199 Japanese Patent Application Publication No. 2015-165301 Japanese Patent Application Publication No. 2010-059235 Japanese Patent Application Publication No. 2019-034998 Japanese Patent Application Publication No. 2021-178918
  • the object of the present invention is to develop a new UV-A or UV-B absorbing material that has excellent absorption properties, specifically absorbs only ultraviolet rays of a specific wavelength, and can be used for general purposes.
  • Our objective is to provide ultraviolet absorbing films, polarizer protective films, polarizing plates, image display devices, transportation equipment, and building material parts.
  • a fluorene compound has excellent ultraviolet absorbing properties for UV-A or UV-B, and is specific for ultraviolet rays of a specific wavelength. It has been found that by adding appropriate substituents to these fluorene compounds, it is possible to absorb ultraviolet rays of various wavelengths. In addition, the inventors discovered that by adding a polymerizable functional group to the above-mentioned fluorene compound, a resin composition having excellent ultraviolet absorption performance could be produced, and the present invention was completed.
  • Z 1a and Z 1b each independently represent an arene ring
  • Y 1a and Y 1b each independently represent a carboxy group, a carboxy ester group, an acid halide group, an acid anhydride group, a hydroxyl group, or a group having a polymerizable double bond
  • R 1a and R 1b are each independently a halogen atom, an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, -R A , -OR A , or -SR A
  • R A is a carbonized (indicates a hydrogen group)
  • k1 and k2 each independently represent an integer of 0 or more
  • m1 and m2 each independently represent an integer of 0 to 4,
  • R 2 is a carbonized (indicates a
  • Y 1a and Y 1b are each independently a group represented by the following formula (Y1), the fluorene compound is a dicarboxylic acid or a derivative thereof, The resin is a polyester resin or a polyamide resin whose constituent unit is the fluorene compound which is a dicarboxylic acid.
  • a 1 represents a linear or branched C 1-6 alkylene group.
  • Y 1a and Y 1b are each independently a group represented by the following formula (Y2), the fluorene compound is a diol,
  • the resin is a polyester resin or a polycarbonate resin whose constituent unit is the fluorene compound which is a diol.
  • the ultraviolet absorber according to any one of [1] to [3].
  • a 2 and A 3 each independently represent a linear or branched C 1-6 alkylene group, p represents an integer of 0 or more.
  • Y 1a and Y 1b are each independently a group represented by the following formula (Y3), the fluorene compound is a diol,
  • the resin is a polyester resin or a polycarbonate resin whose constituent unit is the fluorene compound which is a diol.
  • the ultraviolet absorber according to any one of [1] to [3].
  • Z 2 represents an arene ring
  • a 4 each independently represents a linear or branched C 1-4 alkylene group
  • R 3 each independently represents a substituent
  • q indicates an integer greater than or equal to
  • r represents an integer of 1 or more
  • s represents an integer of 0 or more.
  • Y 3 Z 2 is a fused polycyclic arene ring, The ultraviolet absorber according to [6].
  • Y 1a and Y 1b are each independently a group represented by the following formula (Y4), the fluorene compound is di(meth)acrylate,
  • the resin is a (meth)acrylic resin whose constituent unit is the fluorene compound which is di(meth)acrylate.
  • the ultraviolet absorber according to any one of [1] to [3].
  • a 5 and A 6 each independently represent a linear or branched C 1-6 alkylene group, R 4 represents a hydrogen atom or a methyl group, t represents an integer of 0 or more.
  • the half-width which is the wavelength band showing 1/2 or more of the absorbance at the maximum absorption wavelength, is 55 nm or less, The ultraviolet absorber according to any one of [1] to [8]. [10] It has a maximum absorption wavelength within the wavelength range of 320 to 400 nm, The ultraviolet absorber according to any one of [1] to [9]. [11] The ratio (A 380 /A 400 ) of the molar extinction coefficient at 380 nm (A 380 ) and the molar extinction coefficient at 400 nm (A 400 ) is 50 or more. The ultraviolet absorber according to any one of [1] to [10].
  • the content of the structural unit derived from the fluorene compound is 1 to 100 mol% based on the total structural units of the resin,
  • the ultraviolet absorber according to [1] As the second ultraviolet absorber, at least one compound selected from the group consisting of a triazine ring-containing compound, a benzotriazole ring-containing compound, and a benzophenone ring-containing compound; UV absorbing composition.
  • the ultraviolet absorber according to any one of [1] to [12] any resin;
  • the content of the ultraviolet absorber is 0.1 to 10% by mass based on the total amount, Ultraviolet absorbing resin composition.
  • the ultraviolet shielding layer comprises the ultraviolet absorber according to any one of [1] to [12], the ultraviolet absorbing composition according to [13], or the ultraviolet absorbing resin composition according to [14]. include, UV absorbing coated resin sheet.
  • the ultraviolet shielding layer comprises the ultraviolet absorber according to any one of [1] to [12], the ultraviolet absorbing composition according to [13], or the ultraviolet absorbing resin composition according to [14]. include, UV absorbing coated glass.
  • the spectral transmittance at 350 nm is 5% or less
  • the b* value in L*a*b* color space (CIELAB) is 0.5 or less
  • the spectral transmittance at 380 nm is 8% or less, The polarizer protective film according to [20] or [21].
  • an ultraviolet absorber has excellent ultraviolet absorbing properties for UV-A or UV-B, specifically absorbs only ultraviolet rays of a specific wavelength, and can be used for general purposes.
  • UV-absorbing resins that have excellent bleed-out resistance in addition to the above properties, UV-absorbing coating liquids, UV-absorbing coated resin sheets, UV-absorbing coated glass, UV-absorbing molded bodies, and UV-absorbing Films, polarizer protective films, polarizing plates, image display devices, transportation equipment, and building material parts can be provided.
  • FIG. 1 is a cross-sectional view schematically illustrating a polarizing plate according to an embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of a polarizing plate according to another embodiment of the present invention.
  • 1 is a cross-sectional view schematically illustrating an image display device (OLED) according to an embodiment of the present invention.
  • 1 is a cross-sectional view schematically illustrating an image display device (LCD) according to an embodiment of the present invention.
  • 1 is a cross-sectional view schematically illustrating a rollable display according to an embodiment of the present invention.
  • FIG. 3 is a diagram showing the absorbance of ultraviolet absorbing polyester resins obtained in Examples 8 to 13.
  • the present embodiment an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications can be made without departing from the gist thereof. It is.
  • the same elements are given the same reference numerals, and overlapping explanations will be omitted.
  • the positional relationships such as top, bottom, left, and right are based on the positional relationships shown in the drawings unless otherwise specified.
  • the dimensional ratios in the drawings are not limited to the illustrated ratios.
  • a notation such as “C 2-8” means that the number of carbon atoms in a certain group is 2 or more and 8 or less.
  • the ultraviolet absorber of the present embodiment is a fluorene compound represented by the following general formula (1) or a resin containing a fluorene compound represented by the following general formula (1) as a structural unit.
  • Z 1a and Z 1b each independently represent an arene ring
  • Y 1a and Y 1b each independently represent a carboxy group, a hydroxyl group, or a group having a polymerizable double bond
  • R 1a and R 1b are each independently a halogen atom, an acyl group, a nitro group, a cyano group, an amino group, -R A , -OR A , or -SR A (where R A represents a hydrocarbon group) ) group
  • k1 and k2 each independently represent an integer of 0 or more
  • m1 and m2 each independently represent an integer of 0 to 4
  • R 2a and R 2b each independently represent a substituent
  • n1 and n2 each independently represent an integer of
  • the ultraviolet absorber of this embodiment exhibits excellent ultraviolet absorbency for UV-A or UV-B, and is specific to ultraviolet rays of a specific wavelength. absorb into. Furthermore, the absorption wavelength can be adjusted by changing each group shown in the above general formula (1) into an arbitrary structure.
  • the ultraviolet absorber of this embodiment may be a fluorene compound having a structure represented by general formula (1), or a resin having a structure represented by general formula (1) as a constituent unit. good.
  • Fluorene Compound A fluorene compound has a structure represented by the general formula (1), and includes an arene ring (Z 1a , Z 1b ) bonded to the fluorene ring, which will be explained in detail below, and substituents (Y 1a , Y 1b , R 1a , R 1b , R 2a , R 2b ).
  • Group [-Z 1a -(R 1a ) k1 ] and group [-Z 1b -(R 1b ) k2 ] Z 1a and Z 1b each independently represent an arene ring bonded to a fluorene ring.
  • Such arene rings are not particularly limited, but include, for example, monocyclic arene rings such as benzene rings, fused polycyclic arene rings (fused polycyclic aromatic hydrocarbon rings), ring assembled arene rings (ring assembled polycyclic aromatic hydrocarbon rings).
  • fused polycyclic arene rings are preferred from the viewpoint of molar absorption coefficient in the UV-A region.
  • fused polycyclic arene ring examples include, but are not limited to, a naphthalene ring, an indene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a dibenzochrysene ring, a pyrene ring, Examples include triphenylene ring, corannulene ring, coronene ring, and obalene ring. Among these, a naphthalene ring is preferred.
  • the ring-assembled arene ring is not particularly limited, but includes, for example, bierene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene ring such as terphenyl ring.
  • biphenyl ring is preferred.
  • substitution positions on the fluorene ring of Z 1a and Z 1b are not particularly limited, but are preferably the 2-position and/or the 7-position based on the industrial synthesis method of fluorene compounds.
  • the bonding position of the rings Z 1a and Z 1b to the fluorene skeleton may be either the 1st or 2nd position of the naphthalene ring. good.
  • the first position of the naphthalene ring is preferable.
  • the 2-position of the naphthalene ring is particularly preferable.
  • the number of carbon atoms in Z 1a and Z 1b is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12.
  • the arene rings Z 1a and Z 1b may each independently have non-reactive or non-polymerizable substituents R 1a and R 1b .
  • the substituents R 1a and R 1b are not particularly limited, but include, for example, a halogen atom, an acyl group, a nitro group, a cyano group, a mono- or di-substituted amino group, -R A , -OR A , or -SR A .
  • R A represents a hydrocarbon group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.
  • acyl group examples include C 1-6 alkyl-carbonyl groups such as an acetyl group.
  • Examples of the mono- or di-substituted amino group include dialkylamino group and bis(alkylcarbonyl)amino group.
  • Examples of the dialkylamino group include di-C 1-4 alkylamino groups such as dimethylamino group.
  • Examples of the bis(alkylcarbonyl)amino group include bis(C 1-4 alkyl-carbonyl)amino groups such as diacetylamino group.
  • Examples of the hydrocarbon group represented by R A include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.
  • alkyl group examples include linear or branched C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.
  • alkyl group examples include linear or branched C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group.
  • cycloalkyl group examples include C 5-10 cycloalkyl groups such as cyclopentyl group and cyclohexyl group.
  • Examples of the aryl group include C 6-12 aryl groups such as phenyl group, alkylphenyl group, biphenylyl group, and naphthyl group.
  • Examples of the alkylphenyl group include mono- to tri-C 1-4 alkyl-phenyl groups such as methylphenyl group (or tolyl group) and dimethylphenyl group (or xylyl group).
  • aralkyl group examples include C 6-10 aryl-C 1-4 alkyl groups such as benzyl group and phenethyl group.
  • Examples of the group [-OR A ] include an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, and specifically, groups corresponding to the examples of the hydrocarbon group RA . .
  • alkoxy group examples include linear or branched C 1-10 alkoxy groups such as methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, and t-butoxy.
  • cycloalkyloxy group examples include C 5-10 cycloalkyloxy groups such as cyclohexyloxy group.
  • aryloxy group examples include C 6-10 aryloxy groups such as phenoxy group.
  • aralkyloxy group examples include C 6-10 aryl-C 1-4 alkyloxy groups such as benzyloxy.
  • Examples of the group [-SR A ] include an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, and specific examples include groups corresponding to the examples of the hydrocarbon group R A .
  • alkylthio group examples include C 1-10 alkylthio groups such as methylthio group, ethylthio group, propylthio group, n-butylthio group, and t-butylthio group.
  • cycloalkylthio group examples include C 5-10 cycloalkylthio groups such as cyclohexylthio group.
  • arylthio group examples include C 6-10 arylthio groups such as thiophenoxy group.
  • aralkylthio group examples include C 6-10 aryl-C 1-4 alkylthio groups such as benzylthio group.
  • an alkyl group and an alkoxy group are more preferred, and even more preferred are an alkyl group and an alkoxy group.
  • the group R 1a or R 1b may form a ring assembly arene ring together with the ring Z 1a or Z 1b , respectively.
  • the numbers k1 and k2 of substitution indicate the number of bonds of substituents R 1a and R 1b to arene rings Z 1a and Z 1b .
  • the numbers of substitutions k1 and k2 may be selected depending on the types of arene rings Z 1a and Z 1b .
  • Preferred ranges of the substitution numbers k1 and k2 are, in stages, an integer of 0 to 7, an integer of 0 to 6, an integer of 0 to 5, an integer of 0 to 4, an integer of 0 to 3, an integer of 0 to 2, 0 or 1, and 0.
  • the numbers of substitutions k1 and k2 may be the same or different.
  • the types of the two or more groups R 1a or R 1b substituted on the same ring Z 1a or Z 1b may be the same or different.
  • the types of groups R 1a and R 1b substituting different rings Z 1a and Z 1b may be the same or different.
  • the substitution positions of the groups R 1a and R 1b are not particularly limited, and may be selected depending on the types of the rings Z 1a and Z 1b .
  • the numbers m1 and m2 of substitution are the group [-Z 1a -(R 1a ) k1 ] and the group [-Z 1b -(R 1b ) k2 ] (hereinafter also referred to as "Z 1- containing group") on the fluorene ring. Indicates the number of bonds.
  • the substitution numbers m1 and m2 each independently represent an integer of 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • At least one of m1 and m2 is preferably an integer of 1 or more, more preferably both are integers of 1 or more, and still more preferably both are 1 or more. be.
  • the types of two or more Z1- containing groups substituted on the same benzene ring may be the same or different. You can leave it there.
  • the types of Z 1- containing groups substituted on different benzene rings among the two benzene rings forming the fluorene skeleton that is, the group [-Z 1a -(R 1a ) k1 ] and the group [-Z 1b -(R 1b ) k2 ] may be the same or different.
  • Group R 2a and Group R 2b R 2a and R 2b each independently represent a non-reactive substituent or a non-polymerizable substituent bonded to the fluorene ring.
  • Such a substituent may be any substituent other than the above-mentioned Z 1 -containing group.
  • Such groups R 2a and R 2b include hydrocarbon groups such as alkyl groups and cycloalkyl groups (excluding aryl groups), halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, and cyano groups. Examples include.
  • alkyl group examples include linear or branched C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. can be mentioned. Among these, linear or branched C 1-6 alkyl groups are preferred, and linear or branched C 1-4 alkyl groups such as methyl groups are more preferred.
  • the numbers of substitutions n1 and n2 indicate the number of bonds of substituents R 2a and R 2b to the fluorene ring.
  • the substitution numbers n1 and n2 each independently represent an integer of 0 to 4, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and especially 0. It is. n1 and n2 may be the same or different.
  • n1 or n2 is 2 or more
  • the types of R 2a or R 2b substituted on the same benzene ring may be the same or different. You can leave it there.
  • the types of R 2a and R 2b substituted on different benzene rings may be the same or different.
  • the substitution positions of R 2a and R 2b are not particularly limited, and may be substituted at a position other than the substitution position of the Z 1 -containing group.
  • n1+n1 and m2+n2 are each an integer of, for example, 0 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
  • m1+n1 and m2+n2 may be the same or different.
  • Group Y 1a and Group Y 1b Y 1a and Y 1b are each independently a group bonded to the five-membered ring in the fluorene ring, more specifically to the carbon at the 9-position.
  • Y 1a and Y 1b may be a reactive substituent or a polymerizable substituent having a carboxy group, a hydroxyl group, a polymerizable double bond, or the like.
  • Such Y 1a and Y 1b are not particularly limited, but include, for example, the following formula (Y1), the following formula (Y2), the following formula (Y3), and the following formula (Y4).
  • Formula (Y1) Dicarboxylic acid and derivative thereof Formula (Y1) is shown below.
  • Y 1a and Y 1b are represented by formula (Y1)
  • the fluorene compound of this embodiment may be a dicarboxylic acid or a derivative thereof.
  • a 1 represents a linear or branched alkylene group.
  • dicarboxylic acid derivatives include ester-forming derivatives such as alkyl esters of formula (Y1) (e.g., lower alkyl esters such as methyl ester and ethyl ester), acid halides (e.g., acid chloride, etc.), and acid halides (e.g., acid chlorides).
  • alkyl esters of formula (Y1) e.g., lower alkyl esters such as methyl ester and ethyl ester
  • acid halides e.g., acid chloride, etc.
  • acid halides e.g., acid chlorides
  • Examples of the linear or branched alkylene group represented by A 1 include methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, etc.
  • a linear or branched C 1-6 alkylene group may be mentioned.
  • the number of carbon atoms in A 1 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4.
  • Typical compounds among the dicarboxylic acids and derivatives thereof in which Y 1a and Y 1b are represented by formula (Y1) are not particularly limited, but for example, 9,9-bis(2-carboxyethyl) Fluorene, 9,9-bis(2-carboxypropyl)fluorene, 9,9-bis(carboxyC4-6alkyl)fluorene, 9,9-bis(2-carboxyethyl)2,7-diphenylfluorene, 9,9 -bis(2-carboxypropyl)2,7-diphenylfluorene, 9,9-bis(carboxyC4-6alkyl)2,7-diphenylfluorene, 9,9-bis(2-carboxyethyl)2,7-di (2-naphthyl)fluorene, 9,9-bis(2-carboxypropyl)2,7-di(2-naphthyl)fluorene, 9,9-bis(carboxyC4-6al
  • Formula (Y2) Diol
  • Y2a and Y 1b are represented by formula (Y2)
  • the fluorene compound of this embodiment may be a diol.
  • a 2 and A 3 each independently represent a linear or branched alkylene group, and p represents an integer of 0 or more.
  • Examples of the linear or branched alkylene group represented by A 2 and A 3 include methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetra Examples include linear or branched C 1-6 alkylene groups such as methylene groups. Among these, ethylene group and propylene group are preferred, and ethylene group is particularly preferred.
  • the number of carbon atoms in A 2 and A 3 is preferably 1 to 6, more preferably 2 to 6, and still more preferably 2 to 3.
  • a 2 and A 3 By using such A 2 and A 3 , it has excellent ultraviolet absorption properties for UV-A or UV-B, can specifically absorb only ultraviolet rays of a specific wavelength, and can be used with other resins to be mixed. There is a tendency for the compatibility to improve.
  • the repeating number p of the oxyalkylene group -(A 3 O)- is an integer greater than or equal to 0, and can be selected from the range of about 0 to 20, for example, and preferably from 0 to 15, 0 to 10 in stages. , 0-8, 0-5, 0-3, 0-2, 0-1, especially 0.
  • the number of repetitions p may be an average value (or an arithmetic average value, an arithmetic average value), that is, an average number of added moles, and its range is the same as the range of the above-mentioned integer including preferred embodiments.
  • the two or more types of A 3 in the (poly)oxyalkylene group -(A 3 O) p - may be the same or different, and are preferably the same. .
  • the total number of repeating numbers p in Y 1a and Y 1b that is, the total number of oxyalkylene groups in one molecule of the diol compound represented by formula (1) (or the average value of the total number of added moles) [hereinafter simply [also referred to as the total number of p] can be selected from the range of about 0 to 30, for example, and the preferable range is 0 to 20, 0 to 10, 0 to 6, 0 to 4, 0 to 2 in the following steps. Yes, more preferably 0 to 1, especially 0. Further, the total number of p may be an integer or an average value of the total number of moles.
  • Typical compounds among the above diols in which Y 1a and Y 1b are represented by formula (Y2) are not particularly limited, but for example, m1 and m2 are 1, and Z 1a and Z 1b are benzene, respectively.
  • ring, naphthalene ring, biphenyl ring, etc. A 2 is a linear or branched C 1-6 alkylene group, and A 3 is a linear or branched C 2- 4 alkylene group, and p is 0 or 1 to 10; preferably, m1 and m2 are 1, Z 1a and Z 1b are each a benzene ring or a naphthalene ring, and A 2 is a linear or branched C 1-4 alkylene group, A 3 is a linear or branched C 2-3 alkylene group such as an ethylene group or a propylene group, and p is 0 or 1 to 6 Examples include diol compounds.
  • m1 and m2 are 1, Z 1a and Z 1b are each a naphthalene ring, A 2 is a linear or branched C 2-4 alkylene group, and A 3 is an ethylene group, and p is 0 or 1.
  • 9,9-bis(3-hydroxypropyl)-di(1-naphthyl)fluorene, 9,9-bis(3-hydroxypropyl)-di(2-naphthyl)fluorene, etc. (3-hydroxypropyl)-dinaphthylfluorene is preferred; especially 9,9-bis(3-hydroxypropyl)-dinaphthylfluorene, such as 9,9-bis(3-hydroxypropyl)-2,7-di(2-naphthyl)fluorene. )-2,7-dinaphthylfluorene is preferred.
  • Formula (Y3) Diol Y 1a and Y 1b are shown below.
  • the fluorene compound of this embodiment may be a diol.
  • Z 2 represents an arene ring
  • a 4 each independently represents a linear or branched alkylene group
  • R 3 each independently represents a substituent
  • q is 0 (r indicates an integer greater than or equal to 1, and s indicates an integer greater than or equal to 0.)
  • the arene ring represented by Z 2 is a monocyclic arene ring such as a benzene ring, a fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring), a ring assembly arene ring (ring Examples include aggregated polycyclic aromatic hydrocarbon rings).
  • fused polycyclic arene rings are preferred from the viewpoint of molar absorption coefficient in the UV-A region.
  • fused polycyclic arene ring examples include, but are not limited to, a naphthalene ring, an indene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a dibenzochrysene ring, a pyrene ring, Examples include triphenylene ring, corannulene ring, coronene ring, and obalene ring. Among these, a naphthalene ring is preferred.
  • the ring-assembled arene ring is not particularly limited, but includes, for example, bierene rings such as biphenyl ring, phenylnaphthalene ring, and binaphthyl ring; and terarene ring such as terphenyl ring.
  • biphenyl ring is preferred.
  • the arene ring Z 2 may have a non-reactive or non-polymerizable substituent R 3 .
  • substituent R 3 include hydrocarbon groups such as alkyl groups, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, and cyano groups.
  • alkyl group examples include linear or branched C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, and t-butyl group. can be mentioned. Among these, linear or branched C 1-6 alkyl groups are preferred, and linear or branched C 1-4 alkyl groups such as methyl groups are more preferred.
  • the number of substitutions s indicates the number of bonds of the substituent R 3 to the arene ring Z 2 .
  • the number of substitutions s is, for example, an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly 0.
  • the substitution position of R 3 is not particularly limited, as long as it is substituted at a position other than the substitution position of the group [-(OA 4 ) q -OH].
  • Examples of the linear or branched alkylene group represented by A 4 include methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetramethylene group, etc.
  • a linear or branched C 1-6 alkylene group may be mentioned.
  • the preferable alkylene group A 4 is a linear or branched C 2-6 alkylene group, more preferably a linear or branched C 2-3 alkylene group, especially an ethylene group.
  • a propylene group is preferred, and an ethylene group is particularly preferred.
  • Preferred ranges of the repeating number q of the oxyalkylene group -(OA 4 )- are 0 to 20, 0 to 15, 0 to 10, 0 to 8, 0 to 5, 0 to 3, 0 to 2 in stages. , 0 to 1, 0.
  • the repeating number q may be an average value (or an arithmetic average value, an arithmetic average value), that is, an average number of added moles, and its range is the same as the range of the above-mentioned integer including preferred embodiments.
  • the two or more types of A 4 in the (poly)oxyalkylene group -(OA 4 ) q - may be different from each other, but are preferably the same.
  • the total number of repeating numbers q in Y 1a and Y 1b that is, the total number of oxyalkylene groups in one molecule of the diol compound represented by formula (1) (or the average value of the total number of added moles) [hereinafter simply referred to as [also referred to as the total number of q] can be selected from the range of about 0 to 30, for example, and the preferable range is 0 to 20, 0 to 10, 0 to 6, 0 to 4, 0 to 2 in the following steps. Yes, more preferably 0 to 1, especially 0. Further, the total number of q may be an integer or an average value of the total number of moles.
  • the number of substitutions r indicates the number of bonds of the group [-(OA 4 ) q --OH] to the arene ring Z 2 .
  • the number of substitutions r is, for example, an integer of 1 to 4, preferably an integer of 1 to 2, and more preferably 1.
  • the substitution position of -(OA 4 ) q -OH is not particularly limited, as long as it is substituted at a position other than the substitution position of R 3 .
  • Typical compounds among the above diols in which Y 1a and Y 1b are represented by formula (Y3) are not particularly limited, but for example, m1 and m2 are 0 or 1, Z 1a , Z 1b , Z 2 is a C 6-12 arene ring such as a benzene ring, naphthalene ring, or biphenyl ring, A 4 is a linear or branched C 2-4 alkylene group, and q is 0 or 1 to 10; Preferably, m1 and m2 are 0 or 1, Z 1a , Z 1b , and Z 2 are each a benzene ring or a naphthalene ring, and A 4 is a straight group such as an ethylene group or a propylene group. Examples include diol compounds that are a chain or branched C 2-3 alkylene group and q is 0 or 1 to 6.
  • Formula (Y4) Di(meth)acrylate
  • the following formula (Y4) is shown below.
  • the fluorene compound of this embodiment may be di(meth)acrylate.
  • a 5 and A 6 each independently represent a linear or branched alkylene group, R 4 represents a hydrogen atom or a methyl group, and t represents an integer of 0 or more.
  • Examples of the linear or branched alkylene group represented by A 5 and A 6 include methylene group, ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, 1,3-butanediyl group, tetra Examples include linear or branched C 1-6 alkylene groups such as methylene groups.
  • preferable alkylene groups A 5 and A 6 are linear or branched C 2-6 alkylene groups, more preferably linear or branched C 2-3 alkylene groups, and However, ethylene group and propylene group are preferable, and ethylene group is particularly preferable.
  • the repeating number t of the oxyalkylene group -(A 6 O)- can be selected, for example, from the range of about 0 to 20, and the preferable range is 0 to 15, 0 to 10, 0 to 8, 0 to 5, 0-3, 0-2, 0-1, especially 0.
  • the repetition number t may be an average value (or an arithmetic average value, an arithmetic average value), that is, an average number of added moles, and its range is the same as the range of the above-mentioned integer including preferred embodiments.
  • t is 2 or more, the two or more types of A 6 in the (poly)oxyalkylene group -(A 6 O) t - may be different from each other, but are preferably the same.
  • the substituent represented by R 4 is a hydrogen atom or a methyl group, and when the ultraviolet absorber of this embodiment is used by radical polymerization, it is a hydrogen atom because it has excellent reactivity to radicals. is preferred.
  • Typical compounds among the above di(meth)acrylates in which Y 1a and Y 1b are represented by formula (Y4) are not particularly limited, but for example, 9,9-bis((meth)acryloyl)fluorene , 9,9-bis((meth)acryloyloxyethyl)fluorene, 9,9-bis((meth)acryloyloxymethyl)fluorene, 9,9-bis((meth)acryloyloxypropyl)2,7-diphenylfluorene , 9,9-bis((meth)acryloyloxypropyl)2,7-di(2-naphthyl)fluorene.
  • the di(meth)acrylate components may be used alone or in combination of two or more.
  • the resin of this embodiment contains the fluorene compound represented by the general formula (1) as a structural unit, so it has excellent absorption properties for UV-A or UV-B, and also has excellent absorption properties for specific wavelengths. It can specifically absorb only ultraviolet rays.
  • the resin of this embodiment is not particularly limited, examples thereof include polyester resin, polycarbonate resin, polyamide resin, and acrylic resin. Each resin will be explained in detail below, but the resin of this embodiment is not limited to the following as long as it is included as the structural unit F.
  • Polyester resin A polyester resin is one in which a diol and a dicarboxylic acid are sequentially polymerized to form an ester bond, and a structure derived from a fluorene compound represented by the general formula (1) as at least one or both of the diol and the dicarboxylic acid. It has the unit F.
  • the polyester resin containing the structural unit F is also referred to as "ultraviolet absorbing polyester resin" to distinguish it from other polyester resins.
  • the content of the structural unit F contained in the ultraviolet absorbing polyester resin is preferably 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%, based on the molar ratio of all structural units.
  • the ultraviolet absorbency and the absorption specificity of ultraviolet rays of a specific wavelength tend to be further improved.
  • the diol component of the ultraviolet absorbing polyester resin may be entirely the structural unit F, or may be a combination of the structural unit F, which is a diol component, and another diol component.
  • the structural unit F which is a diol component is not particularly limited, but for example, a structural unit derived from a diol when Y 1a and Y 1b are represented by the formula (Y2), and a structural unit derived from a diol when Y 1a and Y 1b are represented by the formula (Y3). Examples include structural units derived from diols represented by: These diols may be used alone or in combination of two or more.
  • diol components are not particularly limited, but include, for example, at least one diol component selected from the group consisting of aliphatic diols, alicyclic diols, and aromatic diols.
  • aliphatic diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-pentanediol. diols, C 2-8 alkanediols such as 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, polyalkanediols (e.g.
  • diethylene glycol dipropylene glycol, triethylene glycol
  • examples include di- or tri-C 2-4 alkanediols such as Among these, ethylene glycol is particularly preferred since it can improve mechanical properties such as elongation at break and flexibility.
  • alicyclic diols examples include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated aromatic diols such as hydrogenated bisphenol A, which will be exemplified later. can be mentioned.
  • aromatic diols examples include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; Examples include biphenols such as p'-biphenol.
  • diol components may be used alone or in combination of two or more.
  • the dicarboxylic acid component of the ultraviolet absorbing polyester resin may be entirely the structural unit F, or may be a combination of the structural unit F, which is a dicarboxylic acid component, and another dicarboxylic acid component.
  • the structural unit F, which is a dicarboxylic acid component is not particularly limited, but includes, for example, a structural unit derived from a dicarboxylic acid in which Y 1a and Y 1b are represented by formula (Y1). These dicarboxylic acids may be used alone or in combination of two or more.
  • dicarboxylic acid components include, but are not particularly limited to, at least one dicarboxylic acid component selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
  • aliphatic dicarboxylic acids include, but are not limited to, alkanedicarboxylic acids (e.g., C 4-14 alkanedicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid, preferably C 6-12 alkanedicarboxylic acids). acid, etc.), unsaturated aliphatic dicarboxylic acids (for example, C 2-10 alkene-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc.).
  • alkanedicarboxylic acids e.g., C 4-14 alkanedicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid, preferably C 6-12 alkanedicarboxylic acids). acid, etc.
  • unsaturated aliphatic dicarboxylic acids for example, C 2-10 alkene-dicarboxylic acids such as
  • the alicyclic dicarboxylic acid component is not particularly limited, but includes, for example, cycloalkanedicarboxylic acids (for example, C 5-10 cycloalkanedicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid). , di- or tricycloalkanedicarboxylic acids (e.g. decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, etc.), cycloalkenedicarboxylic acids (e.g.
  • C 5-10 cycloalkenes such as cyclohexenedicarboxylic acid) dicarboxylic acid), di- or tricycloalkenedicarboxylic acid (for example, norbornene dicarboxylic acid, etc.), and the like.
  • the aromatic dicarboxylic acid component is not particularly limited, but includes, for example, monocyclic aromatic dicarboxylic acids [e.g., phthalic acid, terephthalic acid, isophthalic acid, alkyl isophthalic acid (e.g., C 1- such as 4-methylisophthalic acid) C 6-10 arene dicarboxylic acids such as 4- alkylisophthalic acids), fused polycyclic aromatic dicarboxylic acids [e.g.
  • arylarene dicarboxylic acid e.g., biphen
  • the dicarboxylic acid component contained in the ultraviolet absorbing polyester resin is not limited to free carboxylic acids, but also ester-forming derivatives of dicarboxylic acids, such as esters [e.g., alkyl esters] lower grades such as methyl esters and ethyl esters. Alkyl esters (eg, C 1-4 alkyl esters, particularly C 1-2 alkyl esters), etc.], acid halides (eg, acid chlorides, etc.), acid anhydrides, and the like. These dicarboxylic acid components may be used alone or in combination of two or more.
  • a UV-absorbing polyester resin can be prepared by reacting a dicarboxylic acid component and a diol component.
  • the method for producing polyester resin is not particularly limited, and it may be prepared by conventional methods, such as melt polymerization methods such as transesterification and direct polymerization, solution polymerization, and interfacial polymerization. Exchange catalysts, polycondensation catalysts, thermal stabilizers, light stabilizers, polymerization modifiers, etc. may also be used.
  • Transesterification catalysts are not particularly limited, but include compounds such as alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cobalt, titanium, etc.) (alkoxides, organic acid salts, inorganic acids, etc.). salts, metal oxides, etc.).
  • alkaline earth metals magnesium, calcium, barium, etc.
  • transition metals manganese, calcium, barium, etc.
  • transition metals manganese acetate, calcium acetate, etc.
  • salts metal oxides, etc.
  • the type of polycondensation catalyst is not particularly limited, and may include alkaline earth metals, transition metals, metals from group 13 of the periodic table (such as aluminum), metals from group 14 of the periodic table (such as germanium), and metals from group 15 of the periodic table (such as antimony). ), more specifically, germanium compounds such as germanium dioxide, germanium hydroxide, germanium oxalate, germanium tetraethoxide, germanium-n-butoxide, antimony trioxide, antimony acetate, antimony ethylene glycolate, etc.
  • Examples include antimony compounds, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, titanium oxalate, titanium potassium oxalate, and other titanium compounds. These catalysts may be used alone or in combination of two or more.
  • heat stabilizer examples include, but are not limited to, phosphorus compounds such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, phosphorous acid, trimethyl phosphite, and triethyl phosphite.
  • the proportions of the dicarboxylic acid component and the diol component to be used can be selected from the same range as described above, and certain components may be used in excess if necessary.
  • a diol component such as ethylene glycol that can be distilled from the reaction system may be used in excess of the proportion of units introduced into the polyester resin.
  • the reaction may be performed in the presence or absence of a solvent.
  • the reaction can be carried out in an inert gas (nitrogen, helium, etc.) atmosphere. Further, the reaction can also be carried out under reduced pressure (for example, about 1 ⁇ 10 2 to 1 ⁇ 10 4 Pa).
  • the reaction temperature may vary depending on the polymerization method. For example, the reaction temperature in the melt polymerization method may be about 150 to 300°C, preferably 180 to 290°C, and more preferably about 200 to 280°C.
  • the glass transition temperature of the ultraviolet absorbing polyester resin is preferably 90 to 190°C, more preferably 100 to 180°C, and even more preferably 110 to 170°C.
  • the glass transition temperature can be measured by the method described in Examples below.
  • the weight average molecular weight of the ultraviolet absorbing polyester resin is preferably 30,000 to 200,000, more preferably 35,000 to 150,000, and still more preferably 40,000 to 110,000.
  • the weight average molecular weight is within the above range, the molecular chain of the ultraviolet absorbing polyester resin is long, and mechanical properties such as elongation at break and flexibility tend to be further improved, and stretchability tends to be further improved.
  • the weight average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). More specifically, it can be measured by the method described in Examples below.
  • a polycarbonate resin is one in which a diol, phosgene, etc. are sequentially polymerized to form a carbonate group, and at least a part of the diol has a structural unit F derived from a fluorene compound represented by the general formula (1).
  • the polycarbonate resin containing the structural unit F is also referred to as "ultraviolet absorbing polycarbonate resin" to distinguish it from other polycarbonates.
  • the structural unit F contained in the ultraviolet absorbing polycarbonate resin preferably has a molar ratio of 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%, based on the total diol units.
  • the content ratio of the ultraviolet absorber is within the above range, ultraviolet absorbency and absorption specificity of ultraviolet rays of a specific wavelength tend to be further improved.
  • the diol component of the ultraviolet absorbing polycarbonate resin may be entirely the structural unit F, or may be a combination of the structural unit F, which is a diol component, and another diol component.
  • the structural unit F which is a diol component is not particularly limited, but for example, a structural unit derived from a diol when Y 1a and Y 1b are represented by the formula (Y2), and a structural unit derived from a diol when Y 1a and Y 1b are represented by the formula (Y3). Examples include structural units derived from diols represented by: These diols may be used alone or in combination of two or more.
  • diol components are not particularly limited, but include, for example, at least one diol component selected from the group consisting of aliphatic diols, alicyclic diols, and aromatic diols.
  • aliphatic diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-pentanediol. diols, C 2-8 alkanediols such as 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, polyalkanediols (e.g. diethylene glycol, dipropylene glycol, triethylene glycol) Among them, ethylene glycol is particularly preferred because it can improve mechanical properties such as elongation at break and flexibility.
  • alicyclic diols examples include cycloalkanediols such as cyclohexanediol; bis(hydroxyalkyl)cycloalkanes such as cyclohexanedimethanol; hydrogenated products of aromatic diols such as hydrogenated products of bisphenol A, etc. Can be mentioned.
  • aromatic diols examples include dihydroxyarenes such as hydroquinone and resorcinol; aromatic aliphatic diols such as benzenedimethanol; bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol C, bisphenol G, and bisphenol S; Examples include biphenols such as p'-biphenol.
  • diol components may be used alone or in combination of two or more.
  • Ultraviolet absorbing polycarbonate resin is prepared by combining a diol component and phosgene or carbonic acid diester (diphenyl carbonate, etc.) by a conventional method, such as a phosgene method (solvent method) or a transesterification method (melt method). It can be produced by reaction (polymerization or condensation).
  • the diol component only needs to contain at least the ultraviolet absorber represented by the general formula (1), and may contain other diol components as necessary. Among these methods, the transesterification method is preferred because it does not require a solvent.
  • the proportion of diester carbonate may be, for example, about 0.8 to 1.5 mol, preferably about 0.9 to 1.2 mol, per 1 mol of the diol component.
  • the transesterification reaction may be performed in the presence of a catalyst.
  • a catalyst include various catalysts used in transesterification reactions, such as nitrogen-containing compounds and metal compounds.
  • nitrogen-containing compounds include quaternary ammonium hydroxides (e.g., tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; trialkylammonium hydroxides such as trimethylbenzylammonium hydroxide); -aralkyl ammonium hydroxide, etc.); tertiary amines (trialkylamines such as trimethylamine and triethylamine; dimethyl-aralkylamines such as dimethylbenzylamine; triarylamines such as triphenylamine), and the like.
  • quaternary ammonium hydroxides e.g., tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide
  • metal compounds examples include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), and Group 13 metals of the periodic table.
  • a metal compound containing a metal such as a group 14 metal of the periodic table (such as germanium), a metal of group 15 of the periodic table (such as antimony) is used. More specifically, examples thereof include alkoxides, organic acid salts (acetates, propionates, etc.), inorganic acid salts (borates, carbonates, etc.), oxides, and hydroxides of the metals.
  • catalysts can be used alone or in combination of two or more.
  • nitrogen-containing compounds such as quaternary ammonium hydroxide are preferred, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide are particularly preferred.
  • the amount of the catalyst used is, for example, about 0.01 x 10 -4 to 100 x 10 -4 mol, preferably about 0.1 x 10 -4 to 40 x 10 -4 mol, per 1 mol of the diol component. Good too.
  • reaction may be carried out in the presence of additives such as stabilizers (antioxidants, heat stabilizers, etc.), if necessary.
  • additives such as stabilizers (antioxidants, heat stabilizers, etc.), if necessary.
  • the reaction can usually be carried out in an inert gas (nitrogen; rare gas such as helium, argon, etc.) atmosphere. Further, the reaction can also be carried out under reduced pressure (for example, about 1 ⁇ 10 2 to 1 ⁇ 10 4 Pa).
  • the reaction temperature can be selected depending on the polymerization method. For example, the reaction temperature in the transesterification method may be, for example, about 150 to 320°C, preferably 200 to 310°C, and more preferably about 250 to 300°C.
  • diphenyl carbonate is used as the carbonic acid diester, it is effective to carry out polycondensation while distilling off phenol at high temperature and under reduced pressure.
  • the glass transition temperature of the ultraviolet absorbing polycarbonate resin is preferably 90 to 190°C, more preferably 100 to 180°C, and still more preferably 110 to 170°C.
  • the glass transition temperature can be measured by the method described in Examples below.
  • the weight average molecular weight of the ultraviolet absorbing polycarbonate resin is preferably 30,000 to 200,000, more preferably 35,000 to 150,000, and even more preferably 40,000 to 110,000.
  • the weight average molecular weight is within the above range, the molecular chain of the ultraviolet absorbing polycarbonate resin is long, and mechanical properties such as elongation at break and flexibility tend to be further improved, and stretchability tends to be further improved.
  • the weight average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). More specifically, it can be measured by the method described in Examples below.
  • Polyamide resin is a product in which diamine and dicarboxylic acid are sequentially polymerized to form an amide bond, and at least a part of the dicarboxylic acid contains a structural unit F derived from a fluorene compound represented by the general formula (1). have Thus, the polyamide resin containing the structural unit F is also referred to as "ultraviolet absorbing polyamide resin" to distinguish it from other polyamides.
  • the structural unit F contained in the ultraviolet absorbing polyamide resin preferably has a molar ratio of 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%, based on the total dicarboxylic acid units.
  • the content ratio of the ultraviolet absorber is within the above range, ultraviolet absorbency and absorption specificity of ultraviolet rays of a specific wavelength tend to be further improved.
  • the dicarboxylic acid component of the ultraviolet absorbing polyamide resin may be entirely the structural unit F, or may be a combination of the structural unit F, which is a dicarboxylic acid component, and another dicarboxylic acid component.
  • the structural unit F, which is a dicarboxylic acid component is not particularly limited, but includes, for example, a structural unit derived from a dicarboxylic acid in which Y 1a and Y 1b are represented by formula (Y1). These dicarboxylic acids may be used alone or in combination of two or more.
  • dicarboxylic acid components are not particularly limited, but include, for example, at least one dicarboxylic acid component selected from the group consisting of aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.
  • aliphatic dicarboxylic acids include, but are not limited to, alkanedicarboxylic acids (e.g., C 4-14 alkanedicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid, preferably C 6-12 alkanedicarboxylic acids). acid, etc.), unsaturated aliphatic dicarboxylic acids (for example, C 2-10 alkene-dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc.).
  • alkanedicarboxylic acids e.g., C 4-14 alkanedicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and decanedicarboxylic acid, preferably C 6-12 alkanedicarboxylic acids). acid, etc.
  • unsaturated aliphatic dicarboxylic acids for example, C 2-10 alkene-dicarboxylic acids such as
  • the alicyclic dicarboxylic acid component is not particularly limited, but includes, for example, cycloalkanedicarboxylic acids (for example, C 5-10 cycloalkanedicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid). , di- or tricycloalkanedicarboxylic acids (e.g. decalindicarboxylic acid, norbornanedicarboxylic acid, adamantanedicarboxylic acid, tricyclodecanedicarboxylic acid, etc.), cycloalkenedicarboxylic acids (e.g.
  • C 5-10 cycloalkenes such as cyclohexenedicarboxylic acid) dicarboxylic acid), di- or tricycloalkenedicarboxylic acid (for example, norbornene dicarboxylic acid, etc.), and the like.
  • the aromatic dicarboxylic acid component is not particularly limited, but includes, for example, monocyclic aromatic dicarboxylic acids [e.g., phthalic acid, terephthalic acid, isophthalic acid, alkyl isophthalic acid (e.g., C 1- such as 4-methylisophthalic acid) C 6-10 arene dicarboxylic acids such as 4- alkylisophthalic acids), fused polycyclic aromatic dicarboxylic acids [e.g.
  • arylarene dicarboxylic acid e.g., biphen
  • dicarboxylic acid components other than the ultraviolet absorber contained in the ultraviolet absorbing polyamide resin are not limited to free carboxylic acids, but also ester-forming derivatives of dicarboxylic acids, such as esters [e.g., alkyl esters [e.g., methyl esters], It also includes lower alkyl esters such as ethyl ester (eg, C 1-4 alkyl esters, particularly C 1-2 alkyl esters), acid halides (eg, acid chlorides), acid anhydrides, and the like. These dicarboxylic acid components may be used alone or in combination of two or more.
  • esters e.g., alkyl esters [e.g., methyl esters]
  • lower alkyl esters such as ethyl ester (eg, C 1-4 alkyl esters, particularly C 1-2 alkyl esters), acid halides (eg, acid chlorides), acid anhydrides, and the like.
  • ethyl ester e
  • Diamine is not particularly limited, and includes, for example, aliphatic diamine, alicyclic diamine, aromatic diamine, and the like. The diamines may be used alone or in combination of two or more.
  • aliphatic diamines examples include alkanediamines (e.g., ethylenediamine, propylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 2 -Methyl-1,5-pentamethylenediamine, 2,2,4-trimethyl-1,6-hexamethylenediamine, 2,4,4-trimethyl-1,6-hexamethylenediamine, 2-methyl-1,8 C 2-20 alkanediamines such as -octamethylene diamine and 5-methyl-1,9-nonamethylene diamine, preferably C 2-12 alkanediamines, and more preferably C 2-8 alkan
  • alicyclic diamine examples include monocyclic cycloalkanediamine, bridged cyclic cycloalkanediamine, and isophorone diamine. Alicyclic diamines may be used alone or in combination of two or more.
  • Examples of the monocyclic cycloalkanediamine include cycloalkanediamines such as diaminocyclohexane (1,4-diaminocyclohexane, etc.), methylcyclohexanediamine (3-methyl-1,4-diaminocyclohexane, etc.); bis(aminomethyl); Examples include cyclohexane (1,4-aminomethylcyclohexane, etc.), bis(aminomethyl)cycloalkanes such as bis(aminomethyl)methylcyclohexane, and the like. Monocyclic cycloalkanediamines are often C4-10 cycloalkanediamines, bis(aminomethyl) C4-10 cycloalkanes.
  • bridged cyclic cycloalkanediamine examples include bi- or tricycloalkanediamine such as bicyclooctanediamine, bicyclononanediamine, tricyclododecanediamine, norbornanediamine; bis(aminomethyl)bicyclooctane, bis(aminomethyl)bicyclononane; , bis(aminomethyl)bi- or tricycloalkanes such as bis(aminomethyl)tricyclododecane and bis(aminomethyl)norbornane.
  • the bridged cyclic cycloalkanediamine is often a C 6-14 bi- or tricycloalkanediamine, a bis(aminomethyl) C 6-14 bi- or tricycloalkane.
  • aromatic diamines examples include arene diamines (e.g., C 6-10 arene diamines such as m-phenylene diamine and p-phenylene diamine), aminoalkyl-amino arenes [e.g., ⁇ -(3-aminophenyl)ethylamine, etc.] amino C 1-4 alkyl-amino C 6-10 arenes], araliphatic diamines [e.g. di(aminoalkyl)arenes (e.g. di(amino C 1-4 alkyl) C 6-10 arene), etc.].
  • Aromatic diamines may be used alone or in combination of two or more.
  • the polymerization component of the ultraviolet absorbing polyamide resin may be composed only of the above-mentioned dicarboxylic acid component and diamine component. aminododecanoic acid, etc.), lactams (epsilon-caprolactam, etc.)] as polymerization components.
  • the ratio of such an aminocarboxylic acid component is, for example, 0.5 mol or less, preferably 0.3 mol or less, more preferably 0.2 mol or less, particularly 0.1 mol or less, per 1 mol of the dicarboxylic acid component. It may be the following.
  • Ultraviolet absorbing polyamide resin can be produced by a conventional method.
  • a polyamide resin can be produced by reacting (polymerizing or condensing) a dicarboxylic acid component and a diamine component.
  • the polymerization method can be selected as appropriate depending on the type of dicarboxylic acid component to be used.
  • a conventional method such as melt polymerization method (or melt polycondensation method, melt mixing of dicarboxylic acid component and diamine component) Examples include the polymerization method described below), solution polymerization method (or solution polycondensation method), and interfacial polymerization method (or interfacial polycondensation method).
  • raw materials such as a salt prepared from a dicarboxylic acid component and a diamine component, a dicarboxylic acid component, and a diamine component are heated to a temperature above their melting point to melt them, and then mixed with water, alcohol, etc.
  • the reaction can be carried out while removing the eliminated component from the reaction system under reduced pressure.
  • the reaction is carried out in a solvent while removing the eliminated component by azeotropy, an acid acceptor such as a tertiary amine, or a condensing agent such as a triphenyl phosphite/pyridine mixed system. I can do it.
  • an acid halide of a dicarboxylic acid is dissolved in a nonpolar solvent, and a reaction with a diamine component can be performed at the interface with an aqueous solution of an alkaline compound such as sodium hydroxide.
  • the salts of the dicarboxylic acid component and the diamine component can be obtained as a precipitate by dissolving each in a solvent and mixing them.
  • the solvent is not particularly limited as long as it can dissolve the dicarboxylic acid component and the diamine component, but examples include ethers (for example, cyclic ethers such as tetrahydrofuran and 1,4-dioxane), ketones ( For example, chain ketones such as methyl ethyl ketone; cyclic ketones such as cyclohexanone), halogen-containing solvents (such as halogenated hydrocarbons such as dichloromethane and chloroform), amides (such as N,N'-dimethylacetamide, N,N'-dimethylformamide, etc.), sulfoxides (eg, dimethyl sulfoxide), nitrogen-containing solvents (eg, N-methylpyrrolidone, etc.),
  • the easily volatilized component may be added in an excessive amount (e.g., 0.01 to 3 mol% or more than the theoretical amount). (in proportion) may be used.
  • the reaction may be carried out under pressure at the initial stage of the reaction.
  • the polymerization reaction may be carried out under normal pressure or reduced pressure, but in the latter stage of polymerization, it is preferable to reduce the pressure to around 150 Pa to promote removal of eliminated components such as water and alcohol from the reaction system.
  • the glass transition temperature of the ultraviolet absorbing polyamide resin can be selected from the range of 120°C or higher (for example, 140°C or higher), for example, 150°C or higher (for example, 160 to 400°C), preferably 165°C or higher. (for example, 165 to 370 °C), more preferably 170 °C or higher (for example, 175 to 350 °C), especially 180 °C or higher (for example, 190 to 320 °C), and 200 °C or higher (for example, 200 °C or higher). to 350°C, preferably 210 to 300°C, more preferably 215 to 280°C).
  • the glass transition temperature can be measured by the method described in Examples below.
  • the weight average molecular weight of the ultraviolet absorbing polyamide resin is preferably 30,000 to 200,000, more preferably 35,000 to 150,000, and even more preferably 40,000 to 110,000.
  • the weight average molecular weight is within the above range, the molecular chain of the ultraviolet absorbing polyamide resin is long, and mechanical properties such as elongation at break and flexibility tend to be further improved, and stretchability tends to be further improved.
  • the weight average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). More specifically, it can be measured by the method described in Examples below.
  • (meth) Acrylic resin is a polymer of (meth) acrylate, and has a structural unit F derived from a fluorene compound represented by the general formula (1) as the (meth) acrylate.
  • the (meth)acrylic resin containing the structural unit F is also referred to as "ultraviolet absorbing (meth)acrylic resin" to distinguish it from other (meth)acrylic resins.
  • the ultraviolet absorber represented by the general formula (1) of the present invention is a reactive di(meth)acrylate, by radical polymerizing it, the ultraviolet absorbent ( It can be made of meth)acrylic resin.
  • the structural unit F contained in the ultraviolet absorbing (meth)acrylic resin is preferably contained in a molar ratio of 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%. preferable.
  • the content ratio of the ultraviolet absorber is within the above range, ultraviolet absorbency and absorption specificity of ultraviolet rays of a specific wavelength tend to be further improved.
  • the (meth)acrylate units of the ultraviolet absorbing (meth)acrylic resin may all be the structural unit F, or may be a combination of the (meth)acrylate structural unit F and other radically polymerizable components. It may be a combination of
  • the structural unit F that is (meth)acrylate is not particularly limited, but includes, for example, a structural unit derived from (meth)acrylate in which Y 1a and Y 1b are represented by formula (Y4). These (meth)acrylates may be used alone or in combination of two or more.
  • radically polymerizable components include, but are not particularly limited to, vinyl compounds, monofunctional (meth)acrylates, polyfunctional (meth)acrylates, and the like.
  • vinyl compounds include aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and vinyltoluene, fatty acid vinyl esters such as vinyl acetate, vinyl propionate, and vinyl pivalate, N-vinylpyrrolidone, and N-vinylacetamide. Examples include N-vinyl compounds.
  • Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates [e.g., C 1-20 alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, etc.] , hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, cyclohexyl (meth)acrylate, aryl (meth)acrylate (e.g., phenyl (meth)acrylate, etc.), aryloxyalkyl (meth)acrylate (e.g., phenoxyethyl (meth)acrylate, etc.) (meth)acrylate, etc.), aralkyl (meth)acrylate (e.g., benzyl (meth)acrylate, etc.), aryloxy((poly)alkoxy)alkyl (meth)acrylate (e.g., phenoxyeth
  • Polyfunctional (meth)acrylates include difunctional (meth)acrylates [for example, C2-10 alkylene glycol di(meth)acrylates such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol polyalkylene glycol di(meth)acrylate such as di(meth)acrylate, di(meth)acrylate of bisphenol A (or its alkylene oxide adduct)], trifunctional or higher functional (meth)acrylate [e.g.
  • (meth)acrylate pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate and other triol or tetraol tri- or tetra(meth)acrylate], oligo(meth)acrylate [urethane(meth)acrylate, epoxy( meth)acrylate, polyester (meth)acrylate, etc.].
  • monofunctional and polyfunctional (meth)acrylates can be used alone or in combination of two or more.
  • Ultraviolet absorbing (meth)acrylic resin can be prepared by reaction of (meth)acrylate.
  • the method for producing the (meth)acrylic resin is not particularly limited, and it may be prepared by a conventional method such as radical polymerization, and a polymerization initiator, photosensitizer, etc. may be used in the polymerization reaction. .
  • the curable composition may contain a polymerization initiator.
  • This polymerization initiator may be a thermal polymerization initiator (thermal radical generator) or a photopolymerization initiator (photoradical generator).
  • thermal polymerization initiator organic peroxides [dialkyl peroxides (e.g., di-tert-butyl peroxide, etc.), diacyl peroxides (e.g., lauroyl peroxide, benzoyl peroxide, etc.), peracids (or peroxyesters) (e.g. tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peracetate, etc.) ketone peroxides, peroxycarbonates, peroxyketals], azo compounds [e.g. 2,2' - Azonitrile compounds such as azobis(isobutyronitrile), azoamide compounds, azoamidine compounds, etc.]. These thermal polymerization initiators can be used alone or in combination of two or more.
  • dialkyl peroxides e.g., di-tert-butyl peroxide, etc.
  • diacyl peroxides e.g., lauroyl per
  • photopolymerization initiators examples include benzoins (benzoin, benzoin alkyl ethers such as benzoin ethyl ether, etc.), acetophenones (acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.), Aminoacetophenones ⁇ 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoaminopropanone-1, etc. ⁇ , anthraquinones (anthraquinone, 2-methylanthraquinone, etc.), thioxanthones (2,4-dimethyl Examples include thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, etc.), ketals (acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.), benzophenones (benzophenone, etc.), and xanthone. These photopolymerization initiators
  • the amount of the polymerization initiator (thermal or photopolymerization initiator) used is 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight (for example, 1 to 10 parts by weight) per 100 parts by weight of the total amount of radically polymerizable components. (8 parts by mass), more preferably about 2 to 5 parts by mass.
  • the photopolymerization initiator may be combined with a photosensitizer.
  • photosensitizers include tertiary amines ⁇ for example, trialkylamine, trialkanolamine (triethanolamine, etc.), ethyl N,N-dimethylaminobenzoate [ethyl p-(dimethylamino)benzoate, etc.] , dialkylaminobenzoic acid alkyl esters such as N,N-amyl dimethylaminobenzoate [p-(dimethylamino)amyl benzoate, etc.], bis(dialkylamino)benzophenones such as 4,4-bis(diethylamino)benzophenone, 4 --(dimethylamino)benzophenone and other dialkylaminobenzophenones ⁇ , and the like.
  • These photosensitizers may be used alone or in combination of two or more.
  • the amount of the photosensitizer used may be about 1 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably about 10 to 100 parts by weight, based on 100 parts by weight of the polymerization initiator.
  • a UV absorber having a di(meth)acrylate structure is easily cured by applying active energy (active energy rays) to produce a UV absorbing (meth)acrylic resin.
  • active energy active energy rays
  • thermal energy and/or light energy are useful.
  • the heating temperature may be, for example, about 50 to 200°C, preferably 60 to 150°C, and more preferably about 70 to 120°C.
  • the amount of light irradiation energy can be selected as appropriate depending on the application, and is, for example, 50 to 10,000 mJ/cm 2 , preferably 70 to 8,000 mJ/cm 2 , more preferably 100 to 8,000 mJ/cm 2 . It may be about 5000 mJ/cm 2 (for example, 500 to 3000 mJ/cm 2 ).
  • Curing may be performed in air or in an inert gas atmosphere (for example, nitrogen, rare gas, etc.).
  • an inert gas atmosphere for example, nitrogen, rare gas, etc.
  • the glass transition temperature of the ultraviolet absorbing (meth)acrylic resin can be selected from the range of -60 to 300 °C, preferably -40 to 250 °C, more preferably about -20 to 200 °C. Good too.
  • the glass transition temperature can be measured by the method described in Examples below.
  • the weight average molecular weight of the ultraviolet absorbing (meth)acrylic resin can be selected from the range of 400 to 15,000 (for example, 600 to 12,000), preferably 800 to 10,000 (for example, 1,000 to 7,500), more preferably 1,200 to 6,000 (for example, 1,500 to 5,000).
  • the weight average molecular weight can be measured in terms of polystyrene by gel permeation chromatography (GPC). More specifically, it can be measured by the method described in Examples below.
  • the fluorene compound of this embodiment and the resin having the structural unit F may be in a crystalline form or in an amorphous form depending on their chemical structure and manufacturing method. There may be. Further, when the ultraviolet absorber takes a crystalline form, a plurality of crystal polymorphs may exist, but when used in the application of the present invention, any form may be used, or a mixture thereof may be used.
  • the half width of the ultraviolet absorber of this embodiment is preferably 55 nm or less, more preferably 50 nm or less, still more preferably 40 nm or less, and even more preferably 30 nm or less.
  • the lower limit of the half width is preferably as small as possible, and is, for example, 3 nm or more.
  • the half-width refers to a wavelength band exhibiting a wavelength width of 1/2 or more of the absorbance, based on the absorption wavelength at which the absorbance is maximum.
  • the ultraviolet absorbent of this embodiment preferably has a maximum absorption wavelength within a wavelength range of 320 to 400 nm.
  • the maximum absorption wavelength is within the above range, it is possible to suitably absorb ultraviolet rays in the long wavelength region, which is generally difficult to absorb.
  • the molar extinction coefficient (A 380 ) at 380 nm is preferably 200 to 2000 L/(mol) cm, more preferably 400 to 1500 L/(mol) cm, and even more preferably 600 to 1000 L/(mol). ⁇ cm.
  • the molar extinction coefficient (A 400 ) at 400 nm is preferably 0.5 to 50 L/(mol) cm, more preferably 1.0 to 25 L/(mol) cm, and even more preferably 2.0 ⁇ 10L/(mol)cm.
  • the molar extinction coefficient (A max ) at the maximum absorption wavelength is preferably 20,000 to 100,000 L/(mol) ⁇ cm, more preferably 30,000 to 90,000 L/(mol) ⁇ cm, and even more preferably 40,000 to 80,000 L/( mol) cm.
  • the excellent UV absorption in the long wavelength region tends to be further improved, and the colorability is further reduced.
  • the ratio (A 380 /A 400 ) of molar extinction coefficient (A 380 ) to molar extinction coefficient (A 400 ) is preferably 50 or more, more preferably 100 or more, and even more preferably 200 or more. Further, the upper limit of the ratio (A 380 /A 400 ) is preferably as large as possible, and is, for example, 1000 or less. When the ratio (A 380 /A 400 ) is 50 or more, it is possible to achieve both excellent UV absorption in the long wavelength region and low coloring property.
  • the melting point of the ultraviolet absorber of the present embodiment may be, for example, about 100 to 250°C, and the preferable ranges are 150 to 240°C, 175 to 230°C, and 180 to 225°C in the following steps.
  • the 5% mass reduction temperature of the ultraviolet absorber of this embodiment may be, for example, about 250 to 500°C, and the preferable ranges are as follows, stepwise: 350 to 480°C, 370 to 450°C, 400 to 430°C. It is °C.
  • the ultraviolet absorbing composition of this embodiment includes the ultraviolet absorber of this embodiment and a triazine ring-containing compound, benzotriazole ring-containing compound, or benzophenone ring-containing compound as a second ultraviolet absorber. It contains at least one kind of compound among them.
  • the ultraviolet absorber of this embodiment may be the above-mentioned fluorene compound, or may be a resin such as ultraviolet absorbing polyester resin, ultraviolet absorbing polycarbonate resin, ultraviolet absorbing polyamide resin, or ultraviolet absorbing (meth)acrylic resin. good. In this way, by mixing the ultraviolet absorber of this embodiment and the second ultraviolet absorber in an arbitrary ratio, it becomes possible to absorb ultraviolet rays having a wider range of wavelengths.
  • the second ultraviolet absorber can be freely selected depending on the desired absorption wavelength, compatibility with the resin described below, etc.
  • the purpose is to absorb ultraviolet light in a wide range of wavelengths in the UV-A region, it is preferable to select a compound containing a triazine ring, and if the purpose is to make it compatible with general-purpose resins, it is preferable to select a compound containing a benzotriazole ring. It is preferable to select a compound, and when the purpose is to make the compound compatible with a resin having low polarity, it is preferable to select a benzophenone ring-containing compound.
  • the proportion of the second ultraviolet absorber contained in the ultraviolet absorbing composition of this embodiment can be freely selected depending on the purpose, but specifically, 0.01 to 50% by mass is preferable.
  • the ultraviolet absorbing resin composition of this embodiment includes the ultraviolet absorbent of this embodiment and an arbitrary resin.
  • the ultraviolet absorber of this embodiment may be the above-mentioned fluorene compound, or may be a resin such as ultraviolet absorbing polyester resin, ultraviolet absorbing polycarbonate resin, ultraviolet absorbing polyamide resin, or ultraviolet absorbing (meth)acrylic resin. good.
  • the content of the ultraviolet absorber of this embodiment is preferably 0.1 to 10% by mass, more preferably 0.5 to 8.0% by mass, based on the total amount of the UV absorbent resin composition. , more preferably 1.0 to 5.0% by mass.
  • the amount of the ultraviolet absorber used is 0.1% by mass or more, the ultraviolet absorption performance tends to be further improved.
  • the amount of the ultraviolet absorber used is 10% by mass or less, physical properties such as rigidity and toughness tend to be further improved.
  • examples of the arbitrary resin include thermoplastic resins and thermosetting resins.
  • the ultraviolet absorbing resin composition can be processed into any form, such as a plate, sheet, or film, as needed.
  • the resin composition used for the ultraviolet absorbing resin composition is preferably a thermoplastic resin because it has excellent moldability and processability.
  • thermoplastic resin is not particularly limited as long as it is compatible with the ultraviolet absorber of this embodiment, but for example, polyolefin resins such as chain olefin resins, cyclic olefin resins (or cycloolefin resins), etc.
  • (meth)acrylic resins such as polystyrene, AS resins, and ABS resins; polyester resins such as polyalkylene arylate resins, polyarylate resins, polyethylene terephthalate, and polycarbonate resins; polyamide resins; triacetyl cellulose, etc.; Examples include cellulose resins; vinyl resins such as polyvinyl chloride, polyvinyl acetate, and polyvinyl alcohol; thermoplastic polyurethane resins, and the like.
  • thermosetting resin is not particularly limited as long as it is compatible with the ultraviolet absorber of this embodiment, but examples include phenol resin; epoxy resin; melamine resin; urea resin; unsaturated polyester resin; alkyd resin; Examples include thermosetting polyurethane resin; thermosetting polyimide resin.
  • Known means can be used to melt and knead the ultraviolet absorbing resin composition, such as a single screw extruder, a twin screw extruder, a Henschel mixer, a Banbury mixer, a tandem mixer, a co-kneader, etc. can be mentioned.
  • a twin-screw extrusion device it is preferable to manufacture by melt-kneading using a twin-screw extrusion device because it allows for uniform and complete mixing.
  • the ultraviolet absorbing resin composition may contain various additives such as fillers or reinforcing agents, coloring agents (dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (oxidizing agents), etc., as necessary. mold release agent, antistatic agent, dispersant, fluidity regulator, leveling agent, antifoaming agent, surface modifier, stress reducing agent (silicone oil, silicone rubber) , various plastic powders, various engineering plastic powders, etc.), heat resistance improvers (sulfur compounds, polysilanes, etc.), carbon materials, etc.]. These additives may be used alone or in combination of two or more.
  • the ultraviolet absorbing coating liquid of this embodiment includes the ultraviolet absorber of this embodiment, the ultraviolet absorbing composition of this embodiment, or the ultraviolet absorbing resin composition of this embodiment, and a solvent. ,including. In this manner, the ultraviolet absorber, ultraviolet absorbing composition, or ultraviolet absorbing resin composition of this embodiment can be dissolved in any solvent to form an ultraviolet absorbing coating liquid.
  • solvents that can be used in the ultraviolet absorbing coating solution include aromatic solvents such as benzene, toluene, and xylene; ketone solvents such as diacetone alcohol, acetone, cyclohexanone, cyclopentanone, methyl ethyl ketone, and methyl isopropyl ketone; Examples include cycloalkane solvents such as cyclohexane, ethylcyclohexane, and 1,2-dimethylcyclohexane; halogen-containing solvents such as methylene chloride and chloroform; and ether solvents such as tetrahydrofuran and dioxane.
  • the concentration of the resin in the coating liquid may be 1% by mass to 50% by mass from the viewpoint of obtaining a viscosity suitable for coating.
  • One type of solvent may be used alone, or two or more types may be used in combination in any ratio.
  • additives such as antifoaming agents, leveling agents, antioxidants, light stabilizers, lubricants, flame retardants, and antistatic agents may be added to the ultraviolet absorbing coating liquid. These additives may be used alone or in combination of two or more.
  • the ultraviolet absorbing coated resin sheet of this embodiment includes a resin sheet and an ultraviolet shielding layer, and the ultraviolet shielding layer includes the ultraviolet absorber of this embodiment, Contains an ultraviolet absorbing composition or an ultraviolet absorbing resin composition. Further, the ultraviolet absorbing coated glass of the present embodiment includes glass and an ultraviolet shielding layer, and the ultraviolet shielding layer contains the ultraviolet absorber, the ultraviolet absorbing composition, or the ultraviolet absorbing resin composition of the present embodiment. include.
  • the resin sheet may be coated with the ultraviolet absorber, ultraviolet absorbing composition, or ultraviolet absorbing resin composition of this embodiment, and is not particularly limited, but may be made of, for example, polycarbonate resin, polyamide resin, polyvinyl alcohol resin, or triacetyl resin.
  • Cellulose ester resins such as cellulose film and cellulose acetate propionate film, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyarylate resins, polyimide resins, cycloolefin resins, polysulfone resins, and polyethersulfone resins.
  • Examples include sheets made of resin, polyolefin resins such as polyethylene and polypropylene, and the like.
  • the glass may be coated with an ultraviolet absorbing coating liquid, and examples include, but are not limited to, float glass, tempered glass, semi-strengthened glass, chemically strengthened glass, green glass, and quartz glass.
  • the ultraviolet absorber, the ultraviolet absorbing composition, or the ultraviolet absorbing resin composition may be applied by applying an ultraviolet absorbing coating liquid to a resin sheet or glass.
  • coating methods include curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, print coating, gravure coating, and die coating. method, gap coating method, and dipping method.
  • drying the ultraviolet absorbing coating liquid there is no restriction on the method of drying the ultraviolet absorbing coating liquid, and for example, drying methods such as heating drying and reduced pressure drying can be used.
  • the ultraviolet absorbing film of this embodiment includes the ultraviolet absorber, ultraviolet absorbing composition, or ultraviolet absorbing resin composition of this embodiment. Moreover, the ultraviolet absorbing molded article of this embodiment contains the ultraviolet absorber, the ultraviolet absorbing composition, or the ultraviolet absorbing resin composition of this embodiment.
  • the ultraviolet absorbing molded article can be made into an ultraviolet absorbing molded article by molding by any method.
  • the shape of the molded article is not particularly limited, and examples include two-dimensional structures such as film, sheet, and plate shapes, and three-dimensional structures such as rod, tube, and hollow shapes.
  • the ultraviolet absorbing molded article of the present invention has excellent optical properties, mechanical properties, and high heat resistance, and is therefore particularly suitable for optical members such as optical films, optical lenses, and optical sheets.
  • the UV-absorbing thermoformed product may contain various additives, such as fillers or reinforcing agents, colorants (dyes and pigments), conductive agents, flame retardants, plasticizers, lubricants, stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, antifoaming agents, surface modifiers, stress reducing agents (silicone oils, silicone rubber, various plastics) powder, various engineering plastic powders, etc.), heat resistance improvers (sulfur compounds, polysilanes, etc.), carbon materials, etc.].
  • additives may be used alone or in combination of two or more.
  • the ultraviolet absorbing molded article can be manufactured using, for example, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, casting molding, and the like.
  • the resin or ultraviolet absorbing resin composition that is the ultraviolet absorber of this embodiment can be formed into a film to form an ultraviolet absorbing film.
  • it may be a single layer film made of only a resin as an ultraviolet absorber or an ultraviolet absorbing resin composition.
  • the method for forming a single layer film is not particularly limited, and examples thereof include solution casting, inflation, melt extrusion such as T-die, and calendering.
  • melt extrusion methods such as the T-die method are preferred from the viewpoint of not only being superior in productivity but also being able to prevent deterioration of optical properties due to residual solvent.
  • the solution casting method is preferable from the viewpoint of being able to form.
  • a coating liquid in which a UV-absorbing polyester resin, a UV-absorbing polycarbonate resin, a UV-absorbing polyamide resin, a UV-absorbing (meth)acrylic resin, or a UV-absorbing resin composition is dissolved in a solvent is applied to the base material.
  • a single layer film can be obtained by peeling off the base material.
  • the base material may be a resin film, a resin sheet, or glass, and from the viewpoint of productivity, a resin film is preferable, and among these, a resin film that has been subjected to a release treatment so that it can be easily peeled off is more preferable.
  • coating methods include curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating, print coating, gravure coating, and die coating. method, gap coating method, and dipping method.
  • drying the coating liquid There is no restriction on the method of drying the coating liquid, and for example, drying methods such as heating drying and reduced pressure drying can be used.
  • the glass transition temperature and melting point of UV-absorbing polyester resin, UV-absorbing polycarbonate resin, UV-absorbing polyamide resin, UV-absorbing (meth)acrylic resin, or UV-absorbing resin composition are Molding conditions can be adjusted accordingly and molding can be carried out by a conventional method.
  • the melting temperature of the extruded resin is preferably Tg+80°C or higher, more preferably Tg+100°C or higher, and preferably Tg+180°C or lower, more preferably Tg+150°C or lower.
  • the above-mentioned melting temperature represents the melting temperature of the resin in an extruder having a T-die.
  • the melting temperature of the extruded resin is equal to or higher than the lower limit of the above range, the fluidity of the resin can be sufficiently increased to improve moldability, and when it is equal to or lower than the upper limit, deterioration of the resin can be suppressed.
  • the ultraviolet absorbing film of the present invention may be not only a single layer film but also a laminated film laminated with other films.
  • the method for forming the laminated film is not particularly limited, and examples thereof include coextrusion, solution casting, extrusion lamination, and the like.
  • the coextrusion molding method is preferred from the viewpoint of not only being excellent in productivity but also being able to prevent deterioration of optical properties and mechanical properties due to residual solvent.
  • the coextrusion T-die method which is a type of coextrusion molding method, includes the feedblock method and the multi-manifold method, but the multi-manifold method is particularly preferred since it can reduce variations in the thickness of each layer.
  • the ultraviolet absorbing film of the present invention may be an unstretched film, but may also be a stretched film from the viewpoint of mechanical properties. Furthermore, stretching treatment is effective as a means of thinning the film.
  • an unstretched film when the thickness is approximately 50 ⁇ m or more, the film thickness can be controlled by nipping with nip rolls after casting from a T-die, and the film thickness accuracy improves. By performing the stretching process by selecting stretching conditions that provide uniform stretching stress, it is possible to obtain a thin film with good film thickness accuracy.
  • Stretching can be performed while heating the ultraviolet absorbing film produced by any of the above methods to an appropriate temperature between the melting point and the glass transition point.
  • Stretching may be biaxial stretching or uniaxial stretching, which can be selected depending on the subsequent embodiment.
  • Biaxial stretching can be performed by stretching the film in both the longitudinal and lateral directions, and the in-plane retardation Ro can be canceled out in the longitudinal and lateral directions to a value close to zero.
  • uniaxial stretching is suitable for use as a film that appropriately exhibits a retardation as required, such as a 1/4 ⁇ retardation film.
  • Polarizer Protective Film The ultraviolet absorbing film of this embodiment can be used as a polarizer protective film.
  • the total thickness of the polarizer protective film is preferably 5 to 90 ⁇ m, more preferably 10 to 80 ⁇ m, and even more preferably 20 to 50 ⁇ m. It can be more suitably used as
  • the spectral transmittance of the polarizer protective film of this embodiment at 350 nm is preferably 5% or less, more preferably 3% or less, and still more preferably 1% or less.
  • the spectral transmittance at a wavelength of 350 nm is within the above range, it is possible to prevent the polarizer from deteriorating due to ultraviolet rays contained in external light, etc., and it can be more suitably used as a polarizer protective film.
  • the b* value in the L*a*b* color space (CIELAB) of the polarizer protective film of this embodiment is preferably 0.8 or less, more preferably 0.6 or less, and even more preferably 0.5 It is as follows. Further, the b* value is preferably -0.8 or more, more preferably -0.6 or more, and even more preferably -0.5 or more. When the b* value is within the above range, a polarizer protective film with excellent visibility can be obtained. Note that the b* value mentioned above is a value calculated according to JIS Z8781-4:2013.
  • the a* value is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 or less. Furthermore, the a* value is preferably -0.4 or more, more preferably -0.3 or more, and still more preferably -0.2 or more.
  • the L* value may preferably be 100 or less, 99 or less, or 98 or less. Further, the L* value is preferably 90 or more, 92 or more, and 94 or more.
  • the spectral transmittance of the polarizer protective film of this embodiment at 380 nm is preferably 8% or less, more preferably 5% or less, and still more preferably 1% or less.
  • the spectral transmittance at a wavelength of 380 nm is within the above range, it is possible to prevent the polarizer from deteriorating due to ultraviolet rays contained in external light, etc., and it can be more suitably used as a polarizer protective film.
  • the polarizing plate of this embodiment includes the polarizer protective film described above, and may further include other layers as necessary. Next, the polarizing plate of this embodiment will be described with reference to FIGS. 1A and 1B. This polarizing plate includes the polarizer protective film of this embodiment.
  • 1A and 1B are cross-sectional views schematically illustrating one embodiment of a polarizing plate.
  • the polarizing plate 20 shown in FIG. 1A has a retardation film 21, a polarizer 23, and a polarizer protective film 10 laminated in this order.
  • an adhesive layer 22 may be provided between the retardation film 21 and the polarizer 23, or an adhesive layer 24 may be provided between the polarizer 23 and the polarizer protective film 10. Good too.
  • the polarizing plate 30 shown in FIG. 1B has a retardation film 31, a polarizer protective film 10, a polarizer 34, and a polarizer protective film 10 laminated in this order.
  • An adhesive layer or adhesive layer 32 may be provided between the retardation film 31 and the polarizer protective film 10, or adhesive layers 33 and 35 may be provided between the polarizer 34 and the polarizer protective film 10. It's okay.
  • the polarizer protective film 10 may be subjected to corona treatment, plasma treatment, or surface modification treatment with a strong base aqueous solution such as sodium hydroxide or potassium hydroxide in order to improve the adhesion with the polarizers 23 and 34.
  • a strong base aqueous solution such as sodium hydroxide or potassium hydroxide
  • These surface modification treatments may be performed after the film forming process or after the stretching process.
  • the polarizers 23 and 34 are not particularly limited as long as they are conventionally known. Molecular films dyed with dichroic substances such as iodine and dichroic dyes and stretched; Polyene-based oriented films such as dehydrated polyvinyl alcohol and dehydrochloric acid treated polyvinyl chloride. Can be mentioned. Also included are polarizers obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it.
  • the above polarizer protective film can be used for the polarizer protective film 10.
  • the polarizer protective film 10 and the polarizers 23 and 34 made of polyvinyl alcohol resin or the like may be bonded together using an ultraviolet curable adhesive (adhesive layers 24, 33, 35).
  • the image display device of this embodiment includes the polarizing plate described above. Next, the image display device of this embodiment will be described with reference to FIGS. 2A and 2B.
  • the image display device of this embodiment is not particularly limited as long as it includes the polarizing plate described above, and examples thereof include an organic electroluminescence (EL) display device and a liquid crystal display device. Further, the image display device is not limited to a device distributed in the market as a single final product, but may be a part of an information processing device described later, such as a smartphone.
  • FIG. 2A is a cross-sectional view schematically illustrating an organic EL display device according to one aspect of the present embodiment
  • FIG. 2B is a cross-sectional view schematically illustrating a liquid crystal display device according to one aspect of the present embodiment. .
  • the organic EL display device 40 includes an organic EL display panel 41, a polarizing plate 20 including the polarizer protective film 10 of this embodiment, and a front plate 43 in this order.
  • the organic EL display device 40 by using the polarizing plate 20 provided with the polarizer protective film 10, it is possible to suppress deterioration of the polarizing plate 20 due to ultraviolet rays and moisture permeation, and also has excellent mechanical strength against bending etc. It is designed to be thinner.
  • the organic EL display device 40 may include other configurations such as a touch sensor 42 as necessary. By being equipped with the touch sensor 42, the organic EL display device 40 functions not only as a display device but also as an information input interface. Each layer constituting the organic EL display device 40 may be bonded using an adhesive or an adhesive.
  • the liquid crystal display device 50 includes a light source 51, a polarizing plate 30, a liquid crystal panel 52, a polarizing plate 30, and a front plate 53 in this order.
  • the light source 51 may be of a direct type in which the light sources are evenly arranged directly under the liquid crystal panel, or may be of an edge light type having a reflector and a light guide plate.
  • the front plate 53 is shown in FIG. 2B, the liquid crystal display device 50 does not need to have the front plate 53.
  • the liquid crystal display device 50 may further include a touch sensor (not shown).
  • the screen of the image display device is not limited to a rectangular shape, and may have a circular, oval, or polygonal shape such as a triangle or a pentagon.
  • the image display device can be flexible and its shape can be changed, such as by being warped, bent, rolled up, or folded.
  • the image display device includes a rollable display that can be used by pulling out an image display device 61 stored in a roll shape in an image display device storage section 62.
  • the ultraviolet-absorbing molded article, ultraviolet-absorbing film, polarizer protective film, polarizing plate, or image display device can be suitably used, for example, as a member of transportation equipment such as automobiles, ships, and aircraft.
  • UV absorber ultraviolet absorbing composition, or ultraviolet absorbing resin composition, ultraviolet absorbing coating liquid, ultraviolet absorbing coated resin sheet, ultraviolet absorbing coated glass, according to the present embodiment
  • Ultraviolet-absorbing molded products, ultraviolet-absorbing films, polarizer protective films, polarizing plates, or image display devices are used in construction materials such as structural materials such as columns and beams, roofing materials, wall materials, flooring materials, and fittings such as doors and windows. It can be used as a member, and in particular, it can be suitably used as a window member for the purpose of absorbing ultraviolet rays that enter during daylighting.
  • Tg Glass transition temperature
  • L*a*b* color space Each film was measured using an ultraviolet-visible spectrophotometer ("V-650" manufactured by JASCO Corporation) in accordance with the regulations of JIS Z8729.
  • V-650 ultraviolet-visible spectrophotometer
  • the L* value represents lightness
  • the a* value and b* value represent hue.
  • DNFDP-m 9,9- Bis(2-methoxycarbonylethyl)-2,7-di(2-naphthyl)fluorene
  • Example 3 Preparation example of DNFPA 30.0 g (0.06 mol) of DNFPO obtained as above, 10.5 g (0.15 mol) of acrylic acid, 55 g of toluene, and 2 - 0.12 g (1.0 mmol) of methoxyphenol was charged. After purging the system with nitrogen and raising the temperature to 95°C to homogenize the components, 1.33 g (7.0 mmol) of p-toluenesulfonic acid monohydrate was added, and after purging with nitrogen again, Dehydrated under reflux for an hour. The reaction temperature was 110-115°C.
  • the obtained solution was washed with 195 g of toluene and 20 g of 20 mass% saline (internal temperature 60 to 70°C), and then washed with 20 g of 10% caustic soda water (10 mass% sodium hydroxide aqueous solution) and 20 g of 20 mass% saline. It was confirmed that the aqueous layer had a pH of 10 or higher. Add 500 mass ppm of 2-methoxyphenol to the entire organic layer, homogenize the solution, and wash twice with 20 g of 20 mass % saline and twice with 20 g of ion-exchanged water (inner temperature 60 to 70°C). It was confirmed that the aqueous layer had a pH of 7.
  • activated carbon FP-6 manufactured by Mizusawa Chemical Co., Ltd.
  • FP-6 manufactured by Mizusawa Chemical Co., Ltd.
  • Example 4 Preparation example of DPFDP-m
  • 192.3 g (0.39 mol) of DBrFDP-m obtained as described above, 150 g (1.2 mol) of phenylboronic acid, and 4.3 L of dimethoxyethane were placed in a reactor.
  • 1 L of 2M sodium carbonate aqueous solution were added, and 22.4 g (19.4 mmol) of tetrakis(triphenylphosphine)palladium(0) [or Pd(PPh3)4] was added under a nitrogen stream to bring the internal temperature to 71-78°C.
  • the mixture was heated under reflux for 5 hours to react.
  • Example 5 Preparation of BNEF In a 1 L separable flask, 45 g of 9-fluorenone (0.25 mol, manufactured by Osaka Gas Chemical Co., Ltd.), 188 g (1 mol) of ethylene glycol mono(2-naphthyl) ether, 3- After adding 1 g of mercaptopropionic acid, it was heated to 60°C to completely dissolve it. Thereafter, 54 g of sulfuric acid was gradually added, and the mixture was stirred for 5 hours while maintaining the temperature at 60° C., and it was confirmed by HPLC (high performance liquid chromatography) that the conversion rate of 9-fluorenone was 99% or more.
  • HPLC high performance liquid chromatography
  • BNEF 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene
  • Example 6 BPEF In Example 6, BPEF:9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, manufactured by Osaka Gas Chemical Co., Ltd., was used as the fluorene compound.
  • Example 7 Preparation of FDP-m 200 ml of 1,4-dioxane and 33.2 g (0.2 mol) of fluorene were placed in a reactor, the fluorene was dissolved by stirring, and the mixture was cooled to 10°C. 3.0 ml of a 40% by mass methanol solution of trimethylbenzylammonium hydroxide (Triton B40, manufactured by Tokyo Kasei Co., Ltd.) was added dropwise, and the mixture was stirred for 30 minutes. Next, 37.9 g (0.44 mol) of methyl acrylate was added and stirred for about 3 hours.
  • Triton B40 trimethylbenzylammonium hydroxide
  • Table 1 shows the evaluation results of the light absorption properties of the various fluorene compounds obtained as described above.
  • Tinuvin 928 Manufactured by BASF
  • ultraviolet absorber LA-F70 Manufactured by ADEKA
  • the fluorene compounds of Examples 1 to 7 all have small half-widths and can selectively absorb only ultraviolet rays in a specific range, and are ultraviolet absorbers that can achieve both excellent UV absorption and low coloration. Met.
  • the fluorene compounds of Examples 1 to 3 have a larger molar extinction coefficient at 380 nm than at 400 nm, so they can achieve both excellent UV absorption and low coloration in the long wavelength region.
  • all of the fluorene compounds had a higher 5% mass loss temperature than the existing benzotriazole ultraviolet absorbers shown in Comparative Example 1, indicating that they had excellent heat resistance.
  • Examples 9-13 As shown in Table 2 below, an ultraviolet absorbing polyester resin was obtained in the same manner as in Example 8, except that the monomer compositions of the diol component and dicarboxylic acid component used were changed.
  • Table 2 shows the ratio of each component in the ultraviolet absorbing polyester resins described in Examples 8 to 13.
  • the UV-absorbing polyester resins of Examples 8 to 13 all have a high ratio of molar extinction coefficient (A 380 ) to molar extinction coefficient (A 400 ) (A 380 /A 400 ), and have excellent UV absorption in the long wavelength region. It was shown that this is a UV absorber that has both good properties and low coloring properties.
  • UV-absorbing polyester resins have a Tg of 130 to 160°C and a weight average molecular weight of 50,000 to 110,000. Furthermore, it was shown that the 5% mass loss temperature was higher than that of conventionally known benzotriazole-based and triazine-based ultraviolet absorbers, and that it also had excellent heat resistance.
  • the ultraviolet absorbing polyester resins obtained in Examples 8 to 13 were dissolved in tetrahydrofuran to prepare 50 mg/L solutions of each, and the absorbance was measured. The evaluation results are shown in Figure 4. As shown in FIG. 4, the ultraviolet absorbing polyester resins of Examples 8 to 13 exhibited high absorbance for ultraviolet light in a wide wavelength band and low absorbance for visible light.
  • Resin composition and film 4.1 Resin composition and film 4.1.
  • PC polycarbonate, Iupilon S-3000, manufactured by Mitsubishi Engineering Plastics Co., Ltd.
  • PMMA polymethyl methacryl
  • the ultraviolet absorbing resin composition obtained as described above is supplied to a twin-screw extruder equipped with a T-die, and a film having the thickness shown in Table 3 below is extruded and wound up as a roll. A film was produced.
  • the evaluation results for each ultraviolet absorbing film are shown in Table 3 below. As shown in Table 3, the ultraviolet absorbing films of Examples 14 to 19 exhibited high ultraviolet absorption performance and low coloration. These ultraviolet absorbing films can be particularly suitably used as polarizer protective films.
  • Examples 20-25 (Preparation of ultraviolet absorbing film)
  • the ultraviolet absorbing polyester resins obtained in Examples 8 to 13 above were supplied to a twin-screw extrusion device equipped with a T-die, a film having a thickness of 50 ⁇ m was extruded and wound up as a roll, and then a tenter stretching device was applied.
  • a UV-absorbing film having the thickness shown in Table 4 below was prepared by simultaneously biaxially stretching the film at a stretching temperature of Tg+10°C.
  • the ultraviolet absorbing films of Examples 17 to 22 exhibited high ultraviolet absorbing performance even if they were thin films of 14 ⁇ m or less.
  • the ultraviolet absorber of the present invention has industrial applicability as a raw material for ultraviolet absorbing coating liquids and compositions, or films obtained using them.

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