WO2018100834A1 - 組成物、光学フィルム、近赤外線カットフィルター、イメージセンサー - Google Patents
組成物、光学フィルム、近赤外線カットフィルター、イメージセンサー Download PDFInfo
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- WO2018100834A1 WO2018100834A1 PCT/JP2017/032774 JP2017032774W WO2018100834A1 WO 2018100834 A1 WO2018100834 A1 WO 2018100834A1 JP 2017032774 W JP2017032774 W JP 2017032774W WO 2018100834 A1 WO2018100834 A1 WO 2018100834A1
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- 0 C1C2CCCC1*2 Chemical compound C1C2CCCC1*2 0.000 description 19
- DCUBAKGEYKVWSX-OYUJONNZSA-N CC(C)(C)C(SC(c1ccccc1)=C1)=C/C1=C(/C)\C(C(C1/C(/C)=C2/C=C(c3ccccc3)SC(C(C)(C)C)=C2)O)C1OC(OC)=O Chemical compound CC(C)(C)C(SC(c1ccccc1)=C1)=C/C1=C(/C)\C(C(C1/C(/C)=C2/C=C(c3ccccc3)SC(C(C)(C)C)=C2)O)C1OC(OC)=O DCUBAKGEYKVWSX-OYUJONNZSA-N 0.000 description 1
- NDCTUULPELJDCZ-SYMFYQLMSA-N CC/C(/C(C(C(C1[O](C)C2)/C2=C2\C(Cl)=C(C(C)(C)C)Nc3ccccc23)O)C1=O)=C1/C(Cl)=C(C(C)(C)C)N(CC)c2c1cccc2 Chemical compound CC/C(/C(C(C(C1[O](C)C2)/C2=C2\C(Cl)=C(C(C)(C)C)Nc3ccccc23)O)C1=O)=C1/C(Cl)=C(C(C)(C)C)N(CC)c2c1cccc2 NDCTUULPELJDCZ-SYMFYQLMSA-N 0.000 description 1
- WJJCAPQYHYRRGG-TULVXVARSA-N CC1(C)c(cccc2)c2N(C)[C@H]1C(C(/C(/C1O)=C(\C2(C)C)/N(C)c3c2cccc3)O)C1=O Chemical compound CC1(C)c(cccc2)c2N(C)[C@H]1C(C(/C(/C1O)=C(\C2(C)C)/N(C)c3c2cccc3)O)C1=O WJJCAPQYHYRRGG-TULVXVARSA-N 0.000 description 1
- ODSUMYWTVRBDPC-UHFFFAOYSA-N CCC(C(C(C1C(CC)=C2C=C(c3ccccc3)SC(c3ccccc3)=C2)OC)C1S)=C1C=C(c2ccccc2)SC(c2ccccc2)=C1 Chemical compound CCC(C(C(C1C(CC)=C2C=C(c3ccccc3)SC(c3ccccc3)=C2)OC)C1S)=C1C=C(c2ccccc2)SC(c2ccccc2)=C1 ODSUMYWTVRBDPC-UHFFFAOYSA-N 0.000 description 1
- YWYXLAQGOGKMFM-ZVKGZHONSA-N CCCCN(c1ccccc1S1)/C1=C(/C(/C(/C1=O)=C2\Sc(cccc3)c3N2CCCC)O)\C1O Chemical compound CCCCN(c1ccccc1S1)/C1=C(/C(/C(/C1=O)=C2\Sc(cccc3)c3N2CCCC)O)\C1O YWYXLAQGOGKMFM-ZVKGZHONSA-N 0.000 description 1
- JCLBHKWRBKPXMC-UHFFFAOYSA-N CCOC(C(C(CC(C1)c2ccccc2N(C2CCCCC2)C1C(C)(C)C)=C1O)=O)=C1O Chemical compound CCOC(C(C(CC(C1)c2ccccc2N(C2CCCCC2)C1C(C)(C)C)=C1O)=O)=C1O JCLBHKWRBKPXMC-UHFFFAOYSA-N 0.000 description 1
- PPPOUQGYYNRBJR-UHFFFAOYSA-N CN(C)c1ccc(C(C(C(C2=O)c(cc3)ccc3N(C)C)O)C2O)cc1 Chemical compound CN(C)c1ccc(C(C(C(C2=O)c(cc3)ccc3N(C)C)O)C2O)cc1 PPPOUQGYYNRBJR-UHFFFAOYSA-N 0.000 description 1
- PAZIQQQEJUTYMR-UHFFFAOYSA-N OC(C(C(C1=O)O)c(cc2CC3)ccc2N3C2CCCCC2)C1c(cc1)cc(CC2)c1N2C1CCCCC1 Chemical compound OC(C(C(C1=O)O)c(cc2CC3)ccc2N3C2CCCCC2)C1c(cc1)cc(CC2)c1N2C1CCCCC1 PAZIQQQEJUTYMR-UHFFFAOYSA-N 0.000 description 1
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/007—Squaraine dyes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/14—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/08—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing alicyclic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/08—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing alicyclic rings
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- C—CHEMISTRY; METALLURGY
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
Definitions
- the present invention relates to a composition containing a squarylium compound or a composition containing a croconium compound, which is preferably used for an image sensor. Moreover, this invention relates to the optical film containing this composition, a near-infrared cut off filter, and an image sensor.
- image (imaging) sensors have a sensitivity in a wide wavelength range.
- an image sensor made of silicon has a sensitivity of up to about 1100 nm.
- an infrared region near infrared region
- image sensors may use different wavelength ranges, and in an environment where multiple sensors use different wavelength ranges, input only specific wave ranges used by each sensor to prevent malfunctions. It is demanded.
- an organic compound having the ability to absorb a specific wavelength range such as near infrared rays is mixed with the constituent material in the image sensor or the imaging optical system, or the specific wavelength Means for adding an optical film having an organic compound having the ability to absorb light are known.
- Patent Document 1 discloses a croconium compound for optical film use having high light resistance, heat resistance and moisture resistance and excellent color tone.
- Patent Document 2 discloses a resin composition having at least one of a carboxylic acid ester and a phosphoric acid ester, a resin, and an infrared absorption property having a squarylium compound. Yes.
- Patent Document 3 includes two or more compounds selected from diimonium compounds, nickel dithiol compounds, phthalocyanine compounds, squarylium compounds, and croconium compounds as near infrared absorbing dyes, one of which is An optical film excellent in storage stability and weather resistance, which is characterized by being a squarylium compound, is disclosed, but in any invention, higher near-infrared absorption stability when irradiated with a specific wavelength for a long time Sex is required.
- JP 2007-169315 A Japanese Patent Laying-Open No. 2015-91923 JP 2007-264384 A
- the present invention has been made in view of the above problems, and an object of the present invention is to provide a composition that contributes to an optical film excellent in near-infrared absorption stability, an optical film containing the composition, a near-infrared cut filter, and an image sensor. Is to provide.
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent. n is 1 or 2. R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not neutral in charge, it has a counter anion. ]
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent.
- n is 1 or 2.
- R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 20 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 20 may further have a substituent. Good. If the molecule is not neutral in charge, it has a counter anion. ]
- composition having a structure different from that of the compound represented by the following general formula 1 and the compound represented by the general formula 1 and including at least one of each of the compounds represented by the following general formula 2.
- a 1 and A 2 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 1 and A 2 may further have a substituent. ]
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent. n is 1 or 2. R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not neutral in charge, it has a counter anion. ]
- a 1 and A 2 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 1 and A 2 may further have a substituent.
- R 10 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 10 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent.
- n is 1 or 2.
- R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 20 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 20 may further have a substituent. Good. If the molecule is not neutral in charge, it has a counter anion. ]
- composition according to claim 1 wherein one of the compounds represented by General Formula 2 includes a compound represented by General Formula 1 below.
- a 1 and A 2 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 1 and A 2 may further have a substituent. ]
- composition according to claim 1 wherein one of the compounds represented by General Formula 5 includes a compound represented by General Formula 3 below.
- a 1 and A 2 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 1 and A 2 may further have a substituent.
- R 10 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 10 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- composition according to claim 1 wherein the compound represented by the general formula 2 includes two compounds represented by the following general formula 6 and the compound represented by the general formula 5 represented by the following general formula 7: object.
- each A 11 and A 21 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 11 and A 21 may further have a substituent. ]
- a 31 and A 41 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 31 and A 41 may further have a substituent.
- R 11 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 11 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- composition according to claim 1 wherein the compound represented by the general formula 2 includes two compounds represented by the following general formula 8 and the compound represented by the general formula 5 represented by the following general formula 9: object.
- a 12 and A 22 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 12 and A 22 may further have a substituent. ]
- each A 32 and A 42 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 32 and A 42 may further have a substituent.
- R 12 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 12 may further have a substituent.
- Good. Ctr ⁇ represents a counter anion.
- composition according to claim 1 wherein A 3 and A 4 in the general formula 2 are represented by the following general formula 10.
- a 5 is a heterocyclic group, and A 5 may further have a substituent.
- R 2 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- composition according to claim 1 wherein A 3 and A 4 in the general formula 5 are represented by the following general formula 10.
- a 5 is a heterocyclic group, and A 5 may further have a substituent.
- R 2 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- composition according to claim 1 wherein A 3 and A 4 in the general formula 2 are represented by the following general formula 11.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.
- R 3 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- Z 1 and Z 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.
- composition according to claim 1, wherein A 3 and A 4 in the general formula 5 are represented by the following general formula 11.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.
- R 3 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- Z 1 and Z 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.
- X 1 is an oxygen atom or a sulfur atom
- Y 1 and Y 2 and Z 1 and Z 2 are selected from the group consisting of a hydrogen atom, a phenyl group, and a tert-butyl group, A composition according to claim 10 or claim 11.
- composition according to claim 1 wherein A 3 and A 4 in the general formula 2 are represented by the following general formula 4.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.
- R 3 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- composition according to claim 1, wherein A 3 and A 4 in the general formula 5 are represented by the following general formula 4.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.
- R 3 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- X 1 is an oxygen atom or a sulfur atom
- Y 1 and Y 2 are selected from the group consisting of a hydrogen atom, a phenyl group, and a tert-butyl group. Composition.
- composition according to claim 16 wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100,000 ppm.
- composition according to claim 19 wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100 ppm.
- a near-infrared cut filter comprising the optical film according to claim 21 and a dielectric multilayer film.
- composition that contributes to an optical film excellent in near-infrared absorption stability and an optical film containing the composition can be provided.
- a and B are diagrams showing a configuration of an optical film according to an embodiment of the present invention.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
- the present inventor made the following estimation in the process of examining the cause of the above-described problems and arrived at the present invention.
- FIG. 1 is a schematic diagram for explaining that entropy is increased by mixing two components.
- FIG. 1A is a mixed model of component A and component B.
- FIG. 1B is a mixed model of components A.
- n added later are different compounds (component B)
- the first compound (component A) is mixed with a different compound (component B), so the entropy increases (FIG. 1A).
- This increase is the entropy effect, and the Gibbs free energy shifts to the minus side, that is, to the stable side, and as a result, the film becomes stable and the change in state over time is reduced as a basic principle. is there.
- This "different compound” makes it possible to effectively suppress compound aggregation over time due to the film stability due to this entropy effect.
- composition is characterized by including at least two compounds represented by the following general formula 2 or the following general formula 5.
- at least one compound represented by the following general formula 1 and at least one compound represented by the following general formula 2 have a structure different from that of the compound represented by the general formula 1.
- a compound represented by the following general formula 5 having a structure different from that of at least one compound represented by the following general formula 3 and the compound represented by the general formula 3 It is a composition containing at least 1 sort (s). More preferably, one of the compounds represented by the following general formula 2 is a composition containing a compound represented by the following general formula 1, or one of the compounds represented by the following general formula 5 is the following general It is a composition containing the compound represented by Formula 3.
- the compound represented by the following general formula 2 is represented by the following general formula 6, and the compound represented by the following general formula 5 includes two kinds of compounds represented by the following general formula 7, or
- the compound represented by the following general formula 2 is a composition containing two compounds represented by the following general formula 8, and the compound represented by the following general formula 5 is represented by the following general formula 9.
- a 1 and A 2 are each independently one or more selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, and A 1 And A 2 may further have a substituent.
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent.
- Q is the same.
- n is 1 or 2.
- R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not neutral in charge, it has a counter anion.
- a 1 and A 2 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 1 and A 2 may further have a substituent.
- R 10 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 10 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- * is a bonding point.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents an alkyl group, a cycloalkyl group or an aryl group.
- R 3 represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- R 3 is preferably a hydrogen atom.
- the movement of the methine chain is suppressed by the interaction between the hydrogen atom and the aromatic group, and the heat resistance is remarkably improved.
- a 3 and A 4 are each independently one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A 3 and A 4 may further have a substituent.
- Q is preferably the same.
- n is 1 or 2.
- R 1 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
- R 20 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 20 may further have a substituent. Good. If the molecule is not neutral in charge, it has a counter anion.
- each A 11 and A 21 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 11 and A 21 may further have a substituent.
- a 31 and A 41 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 31 and A 41 may further have a substituent.
- R 11 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 11 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- a 12 and A 22 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 12 and A 22 may further have a substituent.
- each A 32 and A 42 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A 32 and A 42 may further have a substituent.
- R 12 is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, and an alkoxycarbonyl group, and R 12 may further have a substituent.
- Ctr ⁇ represents a counter anion.
- * is a bonding point.
- a 5 is a heterocyclic group, and A 5 may further have a substituent.
- R 2 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- * is a bonding point.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4
- R 4 represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group.
- R 3 represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.
- Y 1 and Y 2 each independently represent a hydrogen atom, or a substituted or unsubstituted alkyl group or aryl group.
- Z 1 and Z 2 each independently represent a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group.
- a cycloalkyl group having 3 to 30 carbon atoms is preferable, and for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group, and the like are preferable.
- an alkenyl group having 2 to 30 carbon atoms is preferable, and for example, an ethenyl group, an allyl group, a 2-pentenyl group, a 2-ethylbutenyl group, and the like are preferable.
- the alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or 2-butynyl group.
- a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like are preferable.
- a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, and a fluoronyl group are preferable.
- the heterocyclic group includes pyridyl group, pyrimidyl group, furyl ring, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1, 2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazathienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbolyl group ( A carbon atom constituting a carb
- the alkyl group is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, or n-propyl.
- Group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group and the like are preferable.
- a cycloalkyl group having 3 to 30 carbon atoms is preferable, and for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group, and the like are preferable.
- an alkenyl group having 2 to 30 carbon atoms is preferable, and for example, an ethenyl group, an allyl group, a 2-pentenyl group, a 2-ethylbutenyl group, and the like are preferable.
- the alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group or 2-butynyl group.
- a phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group and the like are preferable.
- a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group, and a fluoronyl group are preferable.
- the heterocyclic group includes pyridyl group, pyrimidyl group, furyl ring, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1, 2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazathienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbolyl group ( A carbon atom constituting a carb
- the alkoxycarbonyl group is preferably a straight-chain or branched alkoxycarbonyl group having 1 to 30 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, tert-butoxycarbonyl group. Group, n-octoxycarbonyl group and the like are preferable.
- Ctr ⁇ examples include various inorganic anions and organic anions.
- inorganic anions include halide anions, carbonate anions, bicarbonate anions, sulfate anions, sulfite anions, nitrate anions, nitrite anions, sulfonate anions (such as paratoluene sulfonate), sulfinate anions, phosphate anions, Perfluoroanions (PF 6 ⁇ , BF 4 ⁇ , SbF 6 ⁇ ), peroxide anions (chlorate anion, chlorite anion, hypochlorite anion, bromate anion, iodate anion, etc.) .
- organic anion examples include a carboxylate anion (for example, an acetate anion), an alkoxy anion, an aryloxy anion, and an alkyl sulfonate anion (which may be fluorine-substituted, for example, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, Anions such as nonafluorobutanesulfonic acid), arylsulfonic acid anions (which may have a substituent on the aryl group, such as benzenesulfonic acid, p-toluenesulfonic acid, p-trifluoromethyl) Sulphonic acid, pentafluorobenzene sulphonic acid, naphthalene sulphonic acid and the like anion), alkyl sulphonic acid or aryl sulphonic acid substituted imide anion (for example, bistrifluoromethyl sulphonic acid imide
- Y 1 , Y 2 , Z 1 and Z 2 each represents a substituted or unsubstituted alkyl group or aryl group, and may be bonded to each other to form a ring.
- substituents for Y 1 , Y 2 , Z 1 and Z 2 the substituents listed as the substituents for A 1 to A 5 are preferably used.
- a plurality of substituents may be bonded to each other to form a ring.
- the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, and a benzyl group.
- aryl group examples include a phenyl group and a naphthyl group.
- Y 1 and Y 2 are preferably selected from the group consisting of a substituted or unsubstituted phenyl group and a tert-butyl group from the viewpoint of compound stability.
- X 1 represents an oxygen atom, a sulfur atom or N—R 4 , and R 4 represents an alkyl group, a cycloalkyl group or an aryl group, and X 1 represents an oxygen atom or a sulfur atom particularly from the viewpoint of color. It is preferable.
- the general formula 9 is specifically represented by the following formula.
- a composition comprising a squarylium compound represented by general formula 1 and a squarylium compound represented by general formula 3 or a croconium compound represented by general formula 1 and a general It is a composition comprising a croconium compound represented by Formula 3, and more preferably a composition comprising a squarylium compound represented by Formula 1 and a squarylium compound represented by Formula 3.
- At least two kinds of compounds represented by the general formula 2 or the general formula 5 are mixed and used, but functional materials such as additives and pigments may be mixed, and the additives are preferably oxidized.
- Inhibitors, ultraviolet absorbers, and surfactants, and the dyes are preferably cyanine dyes, nickel chelates, phthalocyanine dyes, and diimmonium dyes.
- the optical film in the present embodiment may be in any form, but in the present embodiment, the optical film includes a composition including at least two compounds represented by the general formula 2 and the general formula 5.
- the structure may be a structure (FIG. 2A) in which a near-infrared absorbing layer formed by coating with a coating solution containing the composition is formed on the substrate surface, or a structure in which the composition is mixed in a resin binder ( FIG. 2B) is also possible.
- the substrate used in the present invention is not particularly limited in the type of glass, plastic and the like, and may be transparent or opaque.
- the support substrate is preferably transparent.
- the transparent support substrate preferably used include glass, quartz, transparent electrodes such as ITO, and transparent resin films.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, cellulose acetate propionate ( CAP), cellulose esters such as cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by J
- the glass substrate is not particularly limited as long as it is a glass substrate containing silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure.
- an absorption glass substrate obtained by adding CuO or the like to a fluorophosphate glass or phosphate glass, a borosilicate glass substrate, a soda glass substrate, a colored glass substrate, an alkali-free glass substrate, a quartz glass substrate, or the like is used.
- glass substrates such as alkali-free glass substrates and low ⁇ -ray glass substrates are preferred.
- an absorption glass substrate is preferable because it has an absorption action in a wide near infrared region of 700 to 1200 nm and the absorption characteristics with respect to obliquely incident light are stable.
- the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.
- the resin used in the present embodiment is not particularly limited, but a resin having excellent heat resistance is preferable.
- the resin having excellent heat resistance include polyimide resins, polyethylene naphthalate resins, polyethersulfone resins, polyether resins, polycarbonates, polyarylates, and cyclic olefin resins. These resins may be used alone or in combination of two or more.
- a resin binder having an aromatic group is preferable because the heat resistance of the compound of the present invention is improved by interacting with the compound of the present invention.
- a polyimide resin is most preferable from the viewpoint of heat resistance.
- semi-alicyclic polyimides such as C3450 manufactured by Mitsubishi Gas Chemical
- aromatic polyimides such as SPIRAREA HR001 manufactured by SOMAR, JL-20 manufactured by Shin Nippon Chemical Co., Ltd.
- aromatic polyimides introduced with fluorine, etc. Can be mentioned.
- Any resin can be added to the resin used in the present embodiment as long as the effects of the present invention are not impaired, and other components such as an antioxidant, an ultraviolet absorber, and a surfactant are added. can do.
- the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane and tetrakis [ Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.
- the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.
- the configuration of the near-infrared absorbing layer is not particularly limited, but is preferably formed by the resin binder, the additive, and the composition.
- the amount of the composition used is appropriately selected according to the desired properties, but is usually 0.01 to 10.0% by mass, preferably 0.00%, based on 100% by mass of the resin used in the present invention.
- the content is 01 to 0.8% by mass, more preferably 0.01 to 5.0% by mass.
- the film thickness of the near infrared absorption layer is usually 20 to 200 ⁇ m, preferably 50 to 100 ⁇ m.
- the thickness is usually 0.1 to 20 ⁇ m, preferably 0.5 to 10 ⁇ m.
- the film thickness is within the above range, a near-infrared absorbing layer having excellent near-infrared absorbing ability and transmittance and strength in the range of 430 to 580 nm can be obtained.
- the solvent used in the present embodiment is not particularly limited, and examples thereof include hydrocarbon solvents, and more preferable examples include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogen solvents. Can be mentioned.
- the aliphatic hydrocarbon solvent include acyclic aliphatic hydrocarbon solvents such as hexane and heptane, cycloaliphatic hydrocarbon solvents such as cyclohexane, alcohol alcohols such as methanol, ethanol, n-propanol, and ethylene glycol.
- Examples include solvents, ketone solvents such as acetone and methyl ethyl ketone, and ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol monomethyl ether.
- Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, cyclohexylbenzene, isopropylbiphenyl, and the like.
- Examples of the halogen solvent include methylene chloride, 1,1,2-trichloroethane, chloroform and the like.
- 2-ethylhexane, sec-butyl ether, 2-pentanol, 2-methyltetrahydrofuran, 2-propylene glycol monomethyl ether, 2,3-dimethyl-1,4-dioxane, sec-butylbenzene, 2 -Methylcyclohexylbenzene and the like can be mentioned.
- methylene chloride and N-methyl-2-pyrrolidone are preferable.
- the other constituent layers constituting the image sensor are not particularly limited.
- dielectric multilayer films A dielectric multilayer film is preferable.
- the dielectric multilayer film is configured by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film.
- the low refractive index and the high refractive index mean having a low refractive index and a high refractive index with respect to the refractive index of the adjacent layer.
- the high refractive index dielectric film preferably has a refractive index (nd) of 1.6 or more, more preferably 2.2 to 2.5.
- the high refractive index dielectric material include Ta 2 O 5 , TiO 2 , Nb 2 O 5 and the like. Of these, TiO 2 is preferable from the viewpoints of film formability, reproducibility in refractive index, and stability.
- the dielectric film having a low refractive index preferably has a refractive index (nd) of less than 1.6, more preferably 1.45 or more and less than 1.55, and even more preferably 1.45 to 1. .47.
- the low refractive index dielectric material include SiO x N y . From the viewpoint of reproducibility of film formation, stability, economy, etc., SiO 2 is desirable.
- the dielectric multilayer film can be produced using, for example, a vacuum film formation process such as a CVD method, a sputtering method, or a vacuum deposition method, or a wet film formation process such as a spray method or a dip method.
- the average transmittance of light having a wavelength of 430 to 620 nm is preferably 90% or more, more preferably 92% or more, and further 95% or more in the spectral transmittance curve at an incident angle of 0 °. preferable.
- the average transmittance of light having a wavelength of 710 to 1100 nm is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less.
- the dielectric multilayer film is preferably 15 or more, more preferably 25 or more, more preferably 30 or more as the total number of laminated layers of the low refractive index dielectric layer and the high refractive index dielectric layer. Is more preferable. However, when the total number of laminated layers increases, the warp of the dielectric multilayer film increases, and the total film thickness increases.
- the film thickness is preferably as small as possible from the viewpoint of reducing the thickness of the optical filter after satisfying the preferred number of layers.
- the film thickness of such a dielectric multilayer film is preferably 2 to 10 ⁇ m.
- Exemplified compound M-35 was synthesized by the same synthesis recipe as exemplified compound M-29 except that ethylmagnesium bromide (1M, THF solution) was used in the synthesis of intermediate C.
- Exemplified compound M-113 was synthesized according to the same synthesis recipe as Exemplified compound M-29 except that 4-methyl-1-octylquinolin-1-ium bromide was used instead of intermediate C.
- the spectral absorption spectrum of the produced film was measured with an ultraviolet-visible spectrophotometer V-570 (manufactured by JASCO Corporation).
- the composition is added to the polyimide resin A so that the resin / composition ratio is 100 parts by mass / 0.1 part by mass, and methylene chloride and ethanol are added so that the solid content concentration becomes 5 wt%. After diluting with a glass plate, this is applied to a glass plate, heated on a 90 ° C. hot plate for 1 hour to evaporate the solvent (methylene chloride and ethanol), and then peeled off the glass plate to obtain a film similar to the above. I was able to.
- the polyimide resin A was synthesized as follows.
- a 200 mL three-necked round bottom flask with all of the stirrer, nitrogen injector, dropping funnel, temperature controller and condenser attached was used as the reactor.
- the reactor was charged with 88.13 g of N, N-dimethylacetamide (DMAc) while passing nitrogen, and 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl (2 , 2′-TFDB) 9.6 g was dissolved. After the reaction temperature was lowered to 10 ° C., 13.32 g of 6-FDA was added thereto, and the solution was allowed to stand at room temperature and stirred for 3 hours.
- DMAc N, N-dimethylacetamide
- 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl 2 , 2′-TFDB
- the polyimide resin prepared by adding the composition was allowed to stand for 600 hours at a temperature of 60 ° C. and a humidity of 90% as an environmental resistance test, and before and after that, a spectral absorption spectrum was measured.
- the near-infrared absorption stability (S1) was calculated and evaluated using the following formula, where the absorbance at the wavelength of ⁇ max before the environmental resistance test was ⁇ 0 and the absorbance at the wavelength after the environmental resistance test was ⁇ 1.
- Formula S1 ⁇ 1 / ⁇ 0 ⁇ 100
- the heat resistance of the polymethyl methacrylate resin prepared by adding the composition was lower than that of the polyimide resin.
- an IR cut filter was produced by forming a polyimide thin film to which a dielectric multilayer film and a dye were added on a glass substrate by the following method.
- Glass substrate A Asahi Glass fluorophosphate glass substrate NF-50TX (hereinafter referred to as “glass substrate A”) having a size of 76 mm ⁇ 76 mm ⁇ 0.214 mm was used with Asahi Glass hydrofluoroether solvent Asahiklin (registered trademark) AE3000 (trade name). Then, it was washed with an ultrasonic cleaner for 10 minutes.
- dielectric multilayer films R near-infrared reflective dielectric multilayer films
- the glass substrate A having the dielectric multilayer film R obtained above was washed again with an ultrasonic cleaner for 20 minutes using the Asahi Glass hydrofluoroether solvent Asahiklin (registered trademark) AE3000.
- a 30 nm layer made of Al 2 O 3 and a 170 nm layer made of SiO 2 are formed using a vacuum deposition apparatus.
- a dielectric layer composed of two layers was formed in this order.
- the refractive index of the layer made of Al 2 O 3 formed was 1.60, and the refractive index of the layer made of SiO 2 formed was 1.45.
- an image sensor was produced using the composition as a mixed color filter, and it functioned as a CMOS sensor and a CCD sensor.
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Abstract
Description
式(1) ΔG=ΔH-TΔS
例えば、ある膜中に2n個の近赤外化合物(成分A)が存在しているとする。その膜が最初は半分の個数のn個の化合物が入っていたところにあとでn個同じ化合物(成分A)が加わって2n個になり体積も2倍になったとする。この時、化合物の種類は同一であるためエントロピーの変化量はゼロである(図1B)。一方、あとで追加されるn個が違う化合物(成分B)だった場合、最初にあった化合物(成分A)は異なる化合物(成分B)が混入してくるためエントロピーは増大する(図1A)。この増大分がエントロピー効果であり、その分だけギブズの自由エネルギーがマイナス側に、すなわち安定側に推移するため、結果として膜は安定となり、経時での状態変化が小さくなるというのが基本原理である。
本発明に係る組成物は、下記一般式2または下記一般式5で表される化合物の少なくとも2種を含むことを特徴としている。好ましくは、下記一般式1で表される化合物の少なくとも1種と、該一般式1で表される化合物とは異なる構造を有し、かつ、下記一般式2で表される化合物の少なくとも1種を含む組成物、または、下記一般式3で表される化合物の少なくとも1種と、該一般式3で表される化合物とは異なる構造を有し、かつ、下記一般式5で表される化合物の少なくとも1種を含む組成物である。より好ましくは、下記一般式2で表される化合物のうち1種は下記一般式1で表される化合物を含む組成物、または、下記一般式5で表される化合物のうち1種は下記一般式3で表される化合物を含む組成物である。さらに好ましくは、下記一般式2で表される化合物が下記一般式6で表され、下記一般式5で表される化合物が下記一般式7で表される2種の化合物を含む組成物、または、下記一般式2で表される化合物が下記一般式8で表され、下記一般式5で表される化合物が下記一般式9で表される2種の化合物を含む組成物である。
本実施形態において、一般式1~一般式11で表される化合物は以下の特徴を有する。
本実施形態における光学フィルムは、どのような形態であってもよいが、前記一般式2及び前記一般式5で表される化合物の少なくとも2種を含む組成物を含む本実施形態において、光学フィルムの構成としては、例えば、基材表面に前記組成物を含む塗布液により塗布形成された近赤外線吸収層を形成する構成(図2A)でもよいし、樹脂バインダーに前記組成物を混合した構成(図2B)でもよい。
本発明に用いられる基板は、ガラス、プラスチック等の種類には特に限定はなく、また透明であっても不透明であってもよい。支持基板側から光を取り出す場合には、支持基板は透明であることが好ましい。好ましく用いられる透明な支持基板としては、ガラス、石英、ITO等の透明電極、透明樹脂フィルムを挙げることができる。樹脂フィルムとしては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)等のポリエステル、ポリエチレン、ポリプロピレン、セロファン、セルロースジアセテート、セルローストリアセテート(TAC)、セルロースアセテートブチレート、セルロースアセテートプロピオネート(CAP)、セルロースアセテートフタレート、セルロースナイトレート等のセルロースエステル類またはそれらの誘導体、ポリ塩化ビニリデン、ポリビニルアルコール、ポリエチレンビニルアルコール、シンジオタクティックポリスチレン、ポリカーボネート、ノルボルネン樹脂、ポリメチルペンテン、ポリエーテルケトン、ポリイミド、ポリエーテルスルホン(PES)、ポリフェニレンスルフィド、ポリスルホン類、ポリエーテルイミド、ポリエーテルケトンイミド、ポリアミド、フッ素樹脂、ナイロン、ポリメチルメタクリレート、アクリルあるいはポリアリレート類、アートン(商品名JSR社製)あるいはアペル(商品名三井化学社製)といったシクロオレフィン系樹脂等を挙げられる。ガラス基板としては、主成分として、珪酸塩を含むガラス基板であれば、特に限定されるものではなく、結晶構造を有する石英ガラス基板等が挙げることができる。ほかに、フツリン酸塩系ガラスやリン酸塩系ガラス等にCuO等を添加した吸収型ガラス基板、ホウ珪酸ガラス基板、ソーダガラス基板、色ガラス基板、無アルカリガラス基板、石英ガラス基板等を用いることができるが、とりわけ、無アルカリガラス基板、低α線ガラス基板等のガラス基板が好ましい。特に吸収型ガラス基板は、広域の近赤外域700~1200nmで吸収作用を有し、斜入射の光に対する吸収特性も安定するため好ましい。不透明な支持基板としては、例えば、アルミ、ステンレス等の金属板、フィルムや不透明樹脂基板、セラミック製の基板等が挙げられる。
本実施形態に用いる樹脂は、特に限定されるものではないが、耐熱性に優れる樹脂が好ましい。耐熱性に優れる樹脂としては、ポリイミド系樹脂、ポリエチレンナフタレート系樹脂、ポリエーテルスルホン系樹脂、ポリエーテル系樹脂、ポリカーボネート、ポリアリレート、及び環状オレフィン系樹脂等を挙げることができる。これらの樹脂は、1種単独でも、2種以上を混合して用いても良い。
本実施形態に用いる樹脂には、本発明の効果を損なわない範囲において、あらゆるものを添加することが可能であるが、さらに酸化防止剤、紫外線吸収剤及び界面活性剤等のその他の成分を添加することができる。酸化防止剤としては、例えば2,6-ジ-t-ブチル-4-メチルフェノール、2,2'-ジオキシ-3,3'-ジ-t-ブチル-5,5'-ジメチルジフェニルメタン及びテトラキス[メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]メタンが挙げられる。
紫外線吸収剤としては、例えば2,4-ジヒドロキシベンゾフェノン及び2-ヒドロキシ-4-メトキシベンゾフェノンが挙げられる。
本実施形態において、近赤外線吸収層の構成は特に限定されるものではないが、前記樹脂バインダーと、前記添加剤と、前記組成物によって形成されるものが好ましい。本発明において、前記組成物の使用量は所望の特性に応じて適宜選択されるが、本発明に用いる樹脂100質量%に対して、通常0.01~10.0質量%、好ましくは0.01~0.8質量%、さらに好ましくは0.01~5.0質量%である。
前記組成物の使用量が上記範囲内にあると、近赤外線吸収能、430~580nmの範囲における透過率及び強度に優れた近赤外線吸収層を得ることができる。
膜厚が上記範囲内にあると、近赤外線吸収能、430~580nmの範囲における透過率及び強度に優れた近赤外線吸収層を得ることができる。
本実施形態に用いる溶媒は、特に限定されるものではないが、炭化水素系溶剤を挙げることができ、より好ましくは脂肪族炭化水素系溶媒、芳香族炭化水素系溶媒、ハロゲン系溶媒を好ましい例として挙げることができる。脂肪族炭化水素系溶媒としては、例えば、ヘキサン、ヘプタン等の非環状脂肪族炭化水素系溶媒、シクロヘキサン等の環状脂肪族炭化水素系溶媒、メタノール、エタノール、n-プロパノール、エチレングリコール等のアルコール系溶媒、アセトン、メチルエチルケトン等のケトン系溶媒、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、1,4-ジオキサン、エチレングリコールモノメチルエーテル等のエーテル系溶媒等が挙げられる。芳香族炭化水素系溶媒としては、例えば、トルエン、キシレン、メシチレン、シクロヘキシルベンゼン、イソプロピルビフェニル等が挙げられる。ハロゲン系溶媒としては、例えば、塩化メチレン、1,1,2-トリクロロエタン、クロロホルム等を挙げることができる。更に具体的には、2-エチルヘキサン、sec-ブチルエーテル、2-ペンタノール、2-メチルテトラヒドロフラン、2-プロピレングリコールモノメチルエーテル、2,3-ジメチル-1,4-ジオキサン、sec-ブチルベンゼン、2-メチルシクロヘキシルベンゼン等を挙げることができる。前記樹脂バインダーを溶解させる観点で、塩化メチレンやN-メチル-2-ピロリドンが好ましい。
本実施形態の一つとして、イメージセンサーを構成するその他の構成層としては、特に限定されるものではないが、例えば撮像素子支持基板、受光部、混在型偏光フィルター、混在型カラーフィルター、マイクロレンズ、誘電体多層膜等が挙げられる。好ましくは、誘電体多層膜である。
高屈折率の誘電体膜は、好ましくは、屈折率(nd)が1.6以上であり、より好ましくは2.2~2.5である。高屈折率の誘電体材料としては、例えば、Ta2O5,TiO2,Nb2O5等が挙げられる。これらのうち、成膜性、屈折率等における再現性、安定性の観点からTiO2が好ましい。
一方、低屈折率の誘電体膜は、好ましくは、屈折率(nd)が1.6未満であり、より好ましくは1.45以上1.55未満であり、よりいっそう好ましくは1.45~1.47である。低屈折率の誘電体材料としては、例えば、SiOxNy等が挙げられる。成膜の再現性、安定性、経済性等の点から、SiO2が望ましい。
誘電体多層膜は、例えば、CVD法、スパッタリング法、真空蒸着法等の真空成膜プロセスや、スプレー法、ディップ法等の湿式成膜プロセス等を使用して作製できる。
本発明に用いる誘電体多層膜は、入射角0°の分光透過率曲線において、波長430~620nmの光の平均透過率は90%以上が好ましく、92%以上がより好ましく、95%以上がさらに好ましい。また、入射角0°の分光透過率曲線において、波長710~1100nmの光の平均透過率は、10%以下が好ましく、8%以下がより好ましく、5%以下がさらに好ましい。さらに、入射角0°の分光透過率曲線において、波長350~430nmに透過率50%となる波長を有し、波長650~750nmに透過率50%となる波長を有するとよい。
この目的のためには、誘電体多層膜は、低屈折率の誘電体層と高屈折率の誘電体層との合計積層数として15層以上が好ましく、25層以上がより好ましく、30層以上がさらに好ましい。ただし、合計積層数が多くなると、誘電体多層膜の反り等が大きくなり、また全体の膜厚が増加するため、100層以下が好ましく、75層以下がより好ましく、60層以下がさらに好ましい。膜厚としては、好ましい積層数を満たした上で、光学フィルターの薄膜化の観点から薄い方が好ましい。このような誘電体多層膜の膜厚としては、2~10μmが好ましい。
下記の化学反応式により、例示化合物M-29を合成した。
水素化ナトリウム28.0gとジエチレングリコールジメチルエーテル(以下、DMEと称す)270mLを混合し、加熱還流を行った。加熱還流下、ベンゾイルアセトン22.8g、ピバル酸エチル27.2g及びDME270mLを混合した溶液を30分かけて滴下した。滴下終了後、加熱還流を4時間行った後、DMEを500mL留去した。反応液を水で冷却し、メタノール30mLをゆっくり加えた。さらに反応溶液を氷水冷却し、水570mLを加え、1時間撹拌を行った。酢酸エチル200mL、濃塩酸68mLを順次加え、有機層を分取した。分取した有機層を硫酸ナトリウムで乾燥させ、減圧濃縮で溶媒を留去することにより中間体Aを30g得た。
濃硫酸450mLを氷水冷却し、中間体Aをトルエン60mLに溶解した溶液を加えた。氷水冷却下、2時間撹拌を行った後、反応溶液を氷水冷却した水5Lに滴下した。滴下終了後、氷水冷却下で2時間撹拌を行い、析出結晶をろ取することにより、中間体Bを18g得た。
窒素雰囲気下、中間体B10gをテトラヒドロフラン(以下、THFと称す)100mLに溶解した。臭化メチルマグネシウム(0.84M、THF溶液)105mLを滴下し、室温で1時間撹拌した。飽和臭化アンモニウム水溶液1Lをゆっくりと加えた後、酢酸エチル500mLを加え、有機層を分取した。有機層を硫酸ナトリウムで乾燥した後、減圧濃縮で溶媒を除去し、中間体Cを6.3g得た。
中間体C6.3g、スクアリン酸1.03g、メタノール28mL、ピリジン1.5gを順次混合し、3時間加熱還流を行った。反応溶液を放冷後、氷水冷却下で5時間撹拌を行い、析出結晶をろ取した。得られた結晶をシリカゲルカラムクロマトグラフィーで精製することにより、例示化合物M-29を1.6g得た。また、シリカゲルカラムクロマトグラフィーで精製することにより、副生成物であるs-5をそれぞれ8mg、s-6を16mg得た。
下記の化学反応式により、例示化合物M-60を合成した。
氷水冷却下、臭化エチルマグネシウム(0.96M、THF溶液)69.3mLに3-メチル-1-ブチン8gを滴下した。滴下終了後、室温で3時間撹拌し、溶液Aとした。
中間体D5.7gをトルエン67mLに溶解し、二酸化マンガン粉末3.6gを加えて40℃で1時間撹拌を行った。反応溶液に二酸化マンガン3.6gを加え、さらに40℃で2時間撹拌を行った。さらに二酸化マンガン3.6gを加え、40℃で3時間撹拌を行った後、二酸化マンガンをろ別した。ろ液を減圧濃縮で留去することにより、中間体Eを5.3g得た。
中間体E5.3gをナトリウムエトキシド(0.05M、エタノール溶液)114mLに溶解し、室温で1時間撹拌を行い、溶液Bとした。
窒素雰囲気下、中間体F5.1gをTHF30mLに溶解した。臭化メチルマグネシウム(0.84M、THF溶液)34mLを滴下し、室温で1時間撹拌した。飽和臭化アンモニウム水溶液120mLをゆっくりと加えた後、酢酸エチル100mLを加え、有機層を分取した。有機層を硫酸ナトリウムで乾燥した後、減圧濃縮で溶媒を留去し、中間体Gを6.2g得た。
中間体G6.2g、クロコン酸1.5g、メタノール35mL、ピリジン1.68gを順次混合し、3時間加熱還流を行った。反応溶液を放冷後、氷水冷却下で5時間撹拌を行い、析出結晶をろ取した。得られた結晶をシリカゲルカラムクロマトグラフィーで精製することにより、例示化合物M-60を1.8g得た。また、シリカゲルカラムクロマトグラフィーで精製することにより、副生成物であるs-17を0.01mg、s-18を0.024g得た。
下記の化学反応式により、例示化合物M-152を合成した。
例示化合物M-6、2.2g、塩化メチレン36mL、ジメチル硫酸3.0g、を順次混合し、6時間加熱還流を行った。反応溶液を放冷後、ソジウムメトキシド(28%メタノール溶液)を3.8g滴下し、室温で4時間撹拌したのちHBF4溶液を滴下し1時間撹拌した。その後有機層を分取し、硫酸ナトリウムで乾燥した後、減圧濃縮で溶媒を留去し、例示化合物M-152を1.5g得た。
ポリイミド系樹脂(SPIXAREA HR001(ソマール(株)製))に前記組成物を樹脂/組成物の比が100質量部/0.12質量部となるように添加し、固形分濃度が5wt%となるようにN-メチル-2-ピロリドンにて希釈した後、これをガラス板に塗布し、90℃のホットプレートで1時間加熱減圧して溶剤(N-メチル-2-ピロリドンに)を蒸発させた後、ガラス板からはがしてフィルムを得た。作製したフィルムの分光吸収スペクトルを、紫外可視分光光度計V-570(日本分光(株)製)にて測定した。
また、ポリイミド系樹脂Aに、前記組成物を、樹脂/組成物の比が100質量部/0.1質量部となるように添加し、固形分濃度が5wt%となるように塩化メチレンとエタノールにて希釈した後、これをガラス板に塗布し、90℃のホットプレートで1時間加熱して溶剤(塩化メチレンとエタノール)を蒸発させた後、ガラス板からはがして前記と同様のフィルムを得ることができた。
ここで、ポリイミド系樹脂Aは、以下のように合成した。
攪拌機、窒素注入装置、滴下漏斗、温度調節器及び冷却器の全てを付着させた、200mL三口丸底フラスコを、反応器として使用した。そして、この反応器に、窒素を通過させながらN,N-ジメチルアセトアミド(DMAc)88.13gを充填した後、2,2’-ビス(トリフルオロメチル)―4,4’-ジアミノビフェニル(2,2’-TFDB)9.6gを溶解した。反応温度を10℃に降温した後、これに6-FDA13.32gを添加して、この溶液を常温で放置して3時間攪拌した。
反応が終わった後、収得されたポリアミド酸溶液にピリジン4.75g、無水酢酸6.13gを投入して、30分攪拌後再び80℃で2時間攪拌して常温で冷やして、これをメタノール1Lが盛られている容器に徐々に投入して沈殿させて、沈殿させた固形分を濾過して粉砕した後、真空中80℃で6時間乾燥して、固形分粉末を乾燥して18.5gのポリイミド系樹脂Aを得た。
前記組成物を10wt%となるようにN-メチル-2-ピロリドンに溶解させ、24時間静置して結晶析出の量(溶液中の全溶質量に対して析出した溶質の量)を評価した。
◎:全く結晶が析出していない
○:析出した結晶が1%未満
△:析出した結晶が5%未満
×:析出した結晶が5%以上
前記組成物を添加して作製したポリイミド系樹脂を、耐環境試験として温度60℃、湿度90%で600時間静置し、その前後で分光吸収スペクトルを測定した。耐環境試験前のλmaxの波長の吸光度をλ0、耐環境試験後の前記波長の吸光度をλ1とし、下記式を用いて近赤外線吸収安定性(S1)を計算し、評価した。
式 S1=λ1/λ0×100
前記組成物の分光吸収スペクトルを測定し、λmaxのときの波長をXnm、一般式1単独のときの分光吸収スペクトルを測定し、λmaxのときの波長をYnmとし、下記式を用いて単独色素の分光吸収スペクトルのλmaxの波長とのずれ(D1)を評価した。
式 D1=|Y-X|
下記表1に示すように前記組成物をそれぞれ用意した。
それぞれの組成物に関して、溶解性、近赤外線吸収安定性(S1)を評価した。結果について、下記表2にまとめて示す。
下記表3に示すように前記組成物をそれぞれ用意した。
それぞれの組成物に関して、溶解性、単独色素の分光吸収スペクトルのλmaxの波長とのずれ(D1)を評価した。結果について、下記表4にまとめて示す。
下記表5に示すように前記組成物をそれぞれ用意した。
それぞれの組成物に関して、溶解性、近赤外線吸収安定性(S1)を評価した。結果について、下記表6にまとめて示す。
下記表7に示すように前記組成物をそれぞれ用意した。
それぞれの組成物に関して、溶解性、単独色素の分光吸収スペクトルのλmaxの波長とのずれ(D1)を評価した。結果について、下記表8にまとめて示す。
76mm×76mm×0.214mmの旭硝子製フツリン酸ガラス基板NF-50TX(以下、ガラス基板Aと呼ぶ。)を、旭硝子製ハイドロフルオロエーテル系溶剤アサヒクリン(登録商標)AE3000(商品名)を用いて、超音波洗浄機で10分間洗浄した。
上記で得られた洗浄したガラス基板Aの一方の主面上に、IAD真空蒸着装置を用いて、高屈折率膜から始めて、高屈折率膜と低屈折率膜を交互に成膜して、合計40層(合計層厚さ:5950nm)の、第1の誘電体多層膜としての近赤外線反射性の誘電体多層膜(以下、誘電体多層膜Rと呼ぶ。)を成膜した。なお、高屈折率材料としてTiO2を用い、低屈折率材料としてSiO2を用いた。
上記で得られた誘電体多層膜Rを有するガラス基板Aを、再び旭硝子製ハイドロフルオロエーテル系溶剤アサヒクリン(登録商標)AE3000を用いて、超音波洗浄機で20分間洗浄した。上記で得られた洗浄したガラス基板Aの誘電体多層膜Rを有する側とは反対側の面に、真空蒸着装置を用いて、Al2O3からなる30nmの層とSiO2からなる170nmの層の2層からなる誘電体層を、この順に成膜した。成膜したAl2O3からなる層の屈折率は1.60、成膜したSiO2からなる層の屈折率は1.45であった。
ポリイミド樹脂として前記ポリイミド樹脂Aの5wt%塩化メチレン/エタノール溶液に、前記組成物をポリイミド樹脂A100質量部に対して1質量部となる割合で混合した後、室温にて攪拌・溶解することで、塗工液を得た。
得られた塗工液を、上記で得られた両主面に誘電体多層膜R及び誘電体層を有するガラス基板Aの誘電体層上にスピンコーターにより塗布し、100℃で5分間加熱乾燥させて、膜厚1μmの近赤外線吸収層を形成した。このようにして、誘電体多層膜R、ガラス基板A、誘電体層、近赤外線吸収層の順に積層された積層体を得た。
Claims (23)
- 下記一般式2または下記一般式5で表される化合物のうち少なくとも2種を含む組成物。
〔一般式2において、A3及びA4はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つである。A3及びA4はさらに置換基を有していてもよい。nは1または2である。R1は水素原子または置換もしくは無置換のアルキル基を表す。分子が電荷的にニュートラルでない場合にはカウンターアニオンを持つ。〕
〔一般式5において、A3及びA4はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つである。A3及びA4はさらに置換基を有していてもよい。nは1または2である。R1は水素原子または置換もしくは無置換のアルキル基を表す。R20は水素原子あるいはアルキル基、シクロアルキル基、アルケニル基、アリール基、複素環基、アルコキシカルボニル基からなる群から選択される1つであり、R20はさらに置換基を有していてもよい。分子が電荷的にニュートラルでない場合にはカウンターアニオンを持つ。〕 - 下記一般式1で表される化合物と、該一般式1で表される化合物とは異なる構造を有し、かつ、下記一般式2で表される化合物のそれぞれ少なくとも一種以上を含む組成物。
〔一般式1において、A1及びA2はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A1及びA2はさらに置換基を有していてもよい。〕
〔一般式2において、A3及びA4はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つである。A3及びA4はさらに置換基を有していてもよい。nは1または2である。R1は水素原子または置換もしくは無置換のアルキル基を表す。分子が電荷的にニュートラルでない場合にはカウンターアニオンを持つ。〕 - 下記一般式3で表される化合物と、該一般式3で表される化合物とは異なる構造を有し、かつ、下記一般式5で表される化合物のそれぞれ少なくとも一種以上を含む組成物。
〔一般式3において、A1及びA2はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A1及びA2はさらに置換基を有していてもよい。R10は水素原子あるいはアルキル基、シクロアルキル基、アルケニル基、アリール基、複素環基、アルコキシカルボニル基からなる群から選択される1つであり、R10はさらに置換基を有していてもよい。Ctr-はカウンターアニオンを表す。〕
〔一般式5において、A3及びA4はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つである。A3及びA4はさらに置換基を有していてもよい。nは1または2である。R1は水素原子または置換もしくは無置換のアルキル基を表す。R20は水素原子あるいはアルキル基、シクロアルキル基、アルケニル基、アリール基、複素環基、アルコキシカルボニル基からなる群から選択される1つであり、R20はさらに置換基を有していてもよい。分子が電荷的にニュートラルでない場合にはカウンターアニオンを持つ。〕 - 前記一般式2で表される化合物が下記一般式6で表され、前記一般式5で表される化合物が下記一般式7で表される、2種の化合物を含む請求項1に記載の組成物。
〔一般式6において、A11及びA21はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A11及びA21はさらに置換基を有していてもよい。〕
〔一般式7において、A31及びA41はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A31及びA41はさらに置換基を有していてもよい。R11は水素原子あるいはアルキル基、シクロアルキル基、アルケニル基、アリール基、複素環基、アルコキシカルボニル基からなる群から選択される1つであり、R11はさらに置換基を有していてもよい。Ctr-はカウンターアニオンを表す。〕 - 前記一般式2で表される化合物が下記一般式8で表され、前記一般式5で表される化合物が下記一般式9で表される、2種の化合物を含む請求項1に記載の組成物。
〔一般式8において、A12及びA22はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A12及びA22はさらに置換基を有していてもよい。〕
〔一般式9において、A32及びA42はそれぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、複素環基からなる群から選択される1つであり、A32及びA42はさらに置換基を有していてもよい。R12は水素原子あるいはアルキル基、シクロアルキル基、アルケニル基、アリール基、複素環基、アルコキシカルボニル基からなる群から選択される1つであり、R12はさらに置換基を有していてもよい。Ctr-はカウンターアニオンを表す。〕 - 前記一般式11において、X1が酸素原子または硫黄原子であり、Y1及びY2及びZ1及びZ2は水素原子、フェニル基、tert-ブチル基からなる群から選択されることを特徴とする請求項10または請求項11に記載の組成物。
- 前記一般式4において、X1が酸素原子または硫黄原子であり、Y1及びY2は水素原子、フェニル基、tert-ブチル基からなる群から選択される請求項13または請求項14に記載の組成物。
- 前記一般式2または前記一般式5で表される化合物の濃度が1ppm~500000ppmであることを特徴とする請求項1~請求項15のいずれか1項に記載の組成物。
- 前記一般式2または前記一般式5で表される化合物の濃度が1ppm~100000ppmであることを特徴とする請求項16に記載の組成物。
- 前記一般式2または前記一般式5で表される化合物の濃度が1ppm~10000ppmであることを特徴とする請求項17に記載の組成物。
- 前記一般式2または前記一般式5で表される化合物の濃度が1ppm~1000ppmであることを特徴とする請求項18に記載の組成物。
- 前記一般式2または前記一般式5で表される化合物の濃度が1ppm~100ppmであることを特徴とする請求項19に記載の組成物。
- 請求項1~請求項20のいずれか1項に記載の組成物を含む光学フィルム。
- 請求項21に記載の光学フィルムと誘電体多層膜とを含む近赤外線カットフィルター。
- 請求項1~請求項20のいずれか1項に記載の組成物を含むイメージセンサー。
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