WO2022045341A1 - 近赤外線透過性黒色材料 - Google Patents
近赤外線透過性黒色材料 Download PDFInfo
- Publication number
- WO2022045341A1 WO2022045341A1 PCT/JP2021/031817 JP2021031817W WO2022045341A1 WO 2022045341 A1 WO2022045341 A1 WO 2022045341A1 JP 2021031817 W JP2021031817 W JP 2021031817W WO 2022045341 A1 WO2022045341 A1 WO 2022045341A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- black material
- group
- infrared
- resin
- oxazine
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims description 37
- 238000002834 transmittance Methods 0.000 claims description 12
- QEQVCPKISCKMOQ-UHFFFAOYSA-N 3h-benzo[f][1,2]benzoxazine Chemical compound C1=CC=CC2=C(C=CNO3)C3=CC=C21 QEQVCPKISCKMOQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 48
- 239000002904 solvent Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 8
- 239000000976 ink Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- -1 t-butoxy group Chemical group 0.000 description 6
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 5
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000001624 naphthyl group Chemical group 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005011 time of flight secondary ion mass spectroscopy Methods 0.000 description 3
- 238000002042 time-of-flight secondary ion mass spectrometry Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DPMZXMBOYHBELT-UHFFFAOYSA-N 1,3,5-trimethyl-1,3,5-triazinane Chemical compound CN1CN(C)CN(C)C1 DPMZXMBOYHBELT-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XOOMNEFVDUTJPP-UHFFFAOYSA-N naphthalene-1,3-diol Chemical compound C1=CC=CC2=CC(O)=CC(O)=C21 XOOMNEFVDUTJPP-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- 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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
Definitions
- the present invention relates to a near-infrared transmissive black material that can sufficiently absorb visible light and sufficiently suppress the absorption of near-infrared rays.
- Patent Document 1 describes an infrared transmissive ink containing a magnetic material, a coloring pigment, and a varnish, and such an ink is said to have excellent concealment.
- the ink of Patent Document 1 has a problem that the effect of suppressing the absorption of near infrared rays is insufficient.
- Infrared transmissive pigments are also used in color filters.
- Color filters are indispensable components for solid-state image sensors and liquid crystal displays.
- color filters for solid-state image sensors are required to have improved color separation and color reproducibility.
- Patent Document 2 describes a composition for a color filter containing a near-infrared transmissive black color material such as a bisbenzofuranone pigment, and such a composition is described. It is said that there is little noise derived from the visible light component.
- the near-infrared transmissive black color material of Cited Document 2 has a problem that the effect of absorbing visible light is insufficient or the absorption of near-infrared rays cannot be sufficiently suppressed.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a near-infrared ray transmissive black material which can sufficiently absorb visible light and sufficiently suppress the absorption of near infrared rays.
- the present invention is a near-infrared transmissive black material containing an oxazine resin.
- the present invention will be described in detail.
- the present inventors have found that the oxazine resin has high transparency in the infrared region while exhibiting brown to black, and has completed the present invention.
- the near-infrared transmissive black material of the present invention contains an oxazine resin.
- an oxazine resin By containing the above-mentioned oxazine resin, it is possible to achieve both absorption of visible light and suppression of absorption of near infrared rays.
- an aromatic oxazine resin having an aromatic ring is preferable.
- the aromatic oxazine resin include a benzoxazine resin having a benzene ring in the basic structure of the resin, a naphthooxazine resin having a naphthalene ring, and the like.
- naphthooxazine resin is preferable because it has high absorbency to visible light and exhibits a higher degree of blackness.
- the benzoxazine resin may have a plurality of benzene rings in the repeating structure. Further, the naphthooxazine resin may have a plurality of naphthalene rings in the repeating structure.
- the oxazine resin is formed by ring-opening polymerization of oxazine, which is a precursor thereof.
- oxazine As the structure of the oxazine, an example of the partial structure of benzoxazine, which is an aromatic oxazine, is shown in the following formula (1), and an example of the partial structure of naphthoxazine is shown in the following formulas (2) and (3).
- R 1 in the formula (1), R 2 in the formula (2), and R 3 in the formula (3) independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or an alkoxy group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and the like.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group and the like.
- the aromatic oxazine has a 6-membered ring added to a benzene ring or a naphthalene ring, and the 6-membered ring contains oxygen and nitrogen, which is the origin of the name.
- R 4 in the formula (4), R 5 in the formula (5), and R 6 in the formula (6) independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, and an alkoxy group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
- the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and the like.
- alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group and the like.
- the oxygen content of the oxazine resin is preferably 5.0% by weight or more, more preferably 10.0% by weight or more, preferably 50.0% by weight or less, and 40.0% by weight. % Or less is preferable. Further, the oxazine resin preferably has a nitrogen content of 0.5% by weight or more, more preferably 1.0% by weight or more, and preferably 20.0% by weight or less. It is more preferably 0% by weight or less.
- the oxygen content and nitrogen content can be measured by, for example, X-ray photoelectron spectroscopy.
- the carbon / oxygen weight ratio in the oxazine resin is preferably 1.0 or more, more preferably 2.0 or more, preferably 30.0 or less, and 25.0 or less. Is more preferable.
- the carbon / nitrogen weight ratio in the oxazine resin is preferably 2.5 or more, more preferably 5.0 or more, preferably 100.0 or less, and 50.0 or less. It is more preferable to have.
- the carbon / oxygen weight ratio and the carbon / nitrogen weight ratio can be measured by, for example, X-ray photoelectron spectroscopy.
- Examples of the method for producing the oxazine resin include a method having a step of reacting a mixed solution containing triazine, dihydroxynaphthalene and a solvent, and a step of reacting a mixed solution containing formaldehyde, an aliphatic amine, dihydroxynaphthalene and a solvent. And the like.
- the naphthooxazine resin can be produced by the above method.
- a benzoxazine resin can be produced by using phenols (for example, phenol, bisphenol, etc.) instead of dihydroxynaphthalene.
- a mixed solution containing triazine, dihydroxynaphthalene and a solvent, and a mixed solution containing formaldehyde, an aliphatic amine, dihydroxynaphthalene and a solvent are prepared.
- formalin which is a formaldehyde solution.
- Formalin usually contains a small amount of methanol as a stabilizer in addition to formaldehyde and water.
- the formaldehyde used in the present invention may be formalin as long as the formaldehyde content is clear. Further, formaldehyde has paraformaldehyde as a polymerization form thereof, which can also be used as a raw material, but since the reactivity is inferior, the above-mentioned formalin is preferably used.
- the aliphatic amine is represented by the general formula R-NH 2 , and R is preferably an alkyl group having 5 or less carbon atoms.
- R is preferably an alkyl group having 5 or less carbon atoms.
- the alkyl group having 5 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and a cyclobutyl group.
- the substituent R is preferably a methyl group, an ethyl group, a propyl group or the like, and as an actual compound name, methylamine, ethylamine, propylamine or the like can be preferably used.
- the most preferred is methylamine, which has the smallest molecular weight.
- dihydroxynaphthalene there are many isomers of the dihydroxynaphthalene.
- 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene are preferable because of their high reactivity.
- 1,5-dihydroxynaphthalene is preferable because it has the highest reactivity.
- the ratio of the three components of dihydroxynaphthalene, aliphatic amine and formaldehyde in the mixed solution is based on 1 mol of dihydroxynaphthalene. Most preferably, 1 mol of aliphatic amine and 2 mol of formaldehyde are blended. Depending on the reaction conditions, the raw material is lost due to volatilization during the reaction, so the optimum compounding ratio is not always exactly the above ratio, but 0.8 to 2.2 aliphatic amines are added to 1 mol of dihydroxynaphthalene.
- mol and formaldehyde in the range of 1.6 to 4.4 mol.
- the amount of the aliphatic amine By setting the amount of the aliphatic amine to 0.8 mol or more, the oxazine ring can be sufficiently formed and the polymerization can be suitably promoted. Further, when the amount is 2.2 mol or less, formaldehyde required for the reaction is not excessively consumed, so that the reaction proceeds smoothly and the desired naphthoxazine can be obtained.
- the formaldehyde to 1.6 mol or more, the oxazine ring can be sufficiently formed and the polymerization can be suitably promoted. Further, it is preferable that the amount is 4.4 mol or less because the occurrence of side reactions can be reduced.
- the mixed solution contains a solvent for dissolving and reacting the two or three raw materials.
- the solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, dioxane, chloroform, ethyl acetate, dimethylformamide, dimethyl sulfoxide and the like.
- the solvent only a single component may be used, or a mixed solvent of two or more kinds may be used.
- a solvent having a solubility parameter (SP value) of 9.0 or more examples include ethanol (12.7), methanol (14.7), isopropanol (11.5), cresol (13.3), ethylene glycol (14.2), and phenol. (14.5), water (23.4), DMF (N, N-dimethylformamide, 12.3), dimethyl sulfoxide (DMSO, 13.0), methyl ethyl ketone (9.3), dioxane (10.3).
- the solvent having an SP value of 9.0 or more a solvent having an SP value of 9.0 to 15.0 is more preferable.
- the boiling point is preferably 50 to 150 ° C. It is more preferable to contain a solvent having a boiling point of 50 to 130 ° C. and an SP value of 9.0 or more.
- the mixed solvent contains a solvent having a boiling point of 150 ° C. or higher, and the content of the solvent having a boiling point of 150 ° C. or higher is 60 volumes. % Or less is preferable. Thereby, a black material having a high average sphericity can be obtained.
- a more preferable lower limit of the content of the solvent having a boiling point of 150 ° C. or higher is 45% by volume.
- the amount of the solvent added to the mixed solution is not particularly limited, but when the raw material (solute) containing dihydroxynaphthalene, triazine, aliphatic amine and formaldehyde is 100 parts by mass, it is usually blended in 300 to 200,000 parts by mass. Is preferable (corresponding to the molar concentration of the solute of 1.0 M to 0.001 M). When the content is 300 parts by mass or more, the solubility of the solute is high, and when the concentration is 200,000 parts by mass or less, the concentration becomes appropriate and the reaction can easily proceed.
- a step of reacting the above-mentioned mixed solution is performed.
- an oxazine resin can be formed.
- the produced oxazine ring opens, and when polymerization occurs, the molecular weight increases, resulting in a so-called oxazine resin.
- the particles are dispersed during the reaction.
- known methods such as stirring, ultrasonic waves, and rotation can be used.
- an appropriate dispersant may be added in order to improve the dispersed state.
- the step of forming the oxazine resin gradually proceeds even at room temperature, but in order to allow the reaction to proceed efficiently, it is preferably performed at a temperature of 50 to 150 ° C.
- the reaction time can be adjusted by the temperature, and is usually preferably 30 minutes to 20 hours.
- spherical oxazine resin particles are obtained.
- the oxazine resin particles obtained in this step show green, brown, or black depending on the reaction conditions.
- the particle size of the oxazine resin particles can be adjusted by parameters such as the concentration of the solution, the reaction temperature, the molar ratio of the raw materials, and the stirring conditions.
- the ring-opening polymerization reaction of oxazine is promoted by heating, in order to sufficiently proceed with the polymerization, it is preferable to heat-treat at 100 to 300 ° C. after performing the above reaction step, and heat treatment at 150 to 250 ° C. It is more preferable to do so.
- the heating time is preferably 30 minutes to 50 hours.
- the atmosphere during heating is preferably an inert gas atmosphere such as nitrogen or argon, and is preferably performed in a closed container in order to suppress evaporation.
- the near-infrared ray transmissive black material of the present invention may contain a binder resin, an ultraviolet absorber, a dispersant and the like in addition to the above-mentioned oxazine resin.
- the near-infrared transmissive black material of the present invention preferably has an average transmittance of 20% or less in the visible light region having a wavelength of 400 to 800 nm. Within the above range, it is possible to sufficiently absorb visible light and develop high blackness.
- the average transmittance is more preferably 15% or less, and further preferably 12% or less.
- the average transmittance can be measured, for example, using a spectrophotometer with an integrating sphere.
- the near-infrared transmissive black material of the present invention preferably has an average transmittance of 60% or more in the near-infrared region having a wavelength of 900 to 2500 nm. Within the above range, the transparency of near infrared rays can be sufficiently enhanced.
- the average transmittance is more preferably 70% or more.
- the average transmittance can be measured, for example, using a spectrophotometer with an integrating sphere.
- the near-infrared transmissive black material of the present invention preferably has a zeta potential (surface potential) of ⁇ 70 to +80 mV. Within the above range, it becomes possible to obtain black particles having excellent particle size uniformity and good dispersibility in a solvent.
- the preferred lower limit of the zeta potential is ⁇ 60 mV, and the preferred upper limit is +70 mV.
- zeta potential for example, a solution in which black particles were dispersed was injected into a measurement cell using a microscope electrophoresis type zeta potential measuring device, and a voltage was applied while observing with a microscope, and the particles did not move (. It can be obtained by measuring the potential at the time of (stationary).
- the near-infrared transmissive black material of the present invention preferably has a density of 1.80 g / cm 3 or less. When the density is 1.80 g / cm 3 or less, high dispersibility can be obtained.
- the preferred lower limit of the density is 1.20 g / cm 3 , and the preferred upper limit is 1.70 g / cm 3 .
- the near-infrared transmissive black material of the present invention preferably has a volume resistivity of 1.0 ⁇ 107 ⁇ ⁇ cm or more.
- the volume resistivity is 1.0 ⁇ 107 ⁇ ⁇ cm or more, high insulation can be ensured. It is more preferably 1.0 ⁇ 10 8 ⁇ ⁇ cm or more, and further preferably 1.0 ⁇ 10 11 ⁇ ⁇ cm or more.
- the preferred upper limit is 1.0 ⁇ 10 18 ⁇ ⁇ cm.
- the near-infrared transmissive black material of the present invention has at least one of a mass spectrum derived from a benzene ring and a mass spectrum derived from a naphthalene ring when measured by time-of-flight secondary ion mass spectrometry (TOF-SIMS). It is preferable that one is detected.
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the shape of the near-infrared ray transmissive black material of the present invention is not particularly limited, and examples thereof include a particle shape, a plate shape, a liquid shape, and the like, and the particle shape is particularly preferable.
- the average particle diameter is preferably 0.01 ⁇ m or more, and preferably 10.0 ⁇ m or less. Within the above range, sufficient blackness and high dispersibility can be obtained.
- the average particle size is more preferably 0.02 ⁇ m or more, and more preferably 5.0 ⁇ m or less.
- the near-infrared transmissive black material of the present invention preferably has a coefficient of variation (CV value) of 20% or less in particle size.
- CV value coefficient of variation
- the CV value (%) of the particle size is the value obtained by dividing the standard deviation by the average particle size as a percentage, and is a numerical value obtained by the following formula. The smaller the CV value, the smaller the variation in particle size.
- CV value of particle size (%) (standard deviation of particle size / average particle size) x 100
- the average particle size and standard deviation can be measured using, for example, FE-TEM.
- the near-infrared transmissive black material of the present invention preferably has an average sphericity of 90% or more. Thereby, the effect of the present invention can be enhanced. A more preferable lower limit of the average sphericity is 95%.
- the degree of spheroidity (minor axis / major axis) can be measured by analyzing an electron micrograph taken by FE-TEM or FE-SEM using an image analyzer, and the average degree of sphericity can be measured. Can be calculated by obtaining the average value of the spherical degree for, for example, 100 particles arbitrarily selected in the electron micrograph.
- the near-infrared transmissive black material of the present invention preferably has a lightness L * value of 30 or less in the CIE LAB (L * a * b *) color system. Within the above range, high blackness can be exhibited.
- the brightness L * is more preferably 25 or less, and further preferably 20 or less.
- the brightness L * can be measured by a spectrocolorimeter according to, for example, JIS Z 8722: 2009.
- Examples of the method for producing the near-infrared ray transmissive black material of the present invention include the same method as the above-mentioned method for producing an oxazine resin.
- the near-infrared transmissive black material of the present invention is used for near-infrared transmissive inks such as coating films, black paints and anti-counterfeit inks, near-infrared transmissive filters such as black matrix for color filters, and near-infrared transmissive films. Can be used for.
- the near-infrared ray transmitting ink and the near infrared ray transmitting filter are also one of the present inventions.
- the present invention it is possible to provide a near-infrared ray transmissive black material which can sufficiently absorb visible light and sufficiently suppress the absorption of near infrared rays.
- Example 1 1.20 g of 1,5-dihydroxynaphthalene (1,5-DHN, manufactured by Tokyo Kasei Co., Ltd.) and 0.98 g of 1,3,5-trimethylhexahydro-1,3,5-triazine (manufactured by Tokyo Kasei Co., Ltd.) It was sequentially dissolved in 50 ml of ethanol to prepare an ethanol mixed solution. Next, the obtained mixed solution was heated and stirred at 80 ° C. for 5.0 hours (rotation speed: 300 rpm). The solution is filtered through a glass filter, washed 3 times with ethanol, vacuum dried at 50 ° C. for 3 hours, and further vacuum heated at 200 ° C.
- a naphthooxazine resin as a near-infrared transmissive black material. Obtained particles. 4 parts by weight of the obtained black material was dispersed in 40 parts by weight of polyvinyl butyral resin, coated on a slide glass so as to have a thickness of 30 ⁇ m after drying, and dried at 100 ° C. for 2 hours to obtain a coating film. rice field.
- the particles were recovered, washed, vacuum dried at 50 ° C. for 3 hours, and further heat-treated at 220 ° C. for 20 hours to obtain naphthooxazine resin particles as a near-infrared ray transmissive black material.
- a coating film was prepared in the same manner as in Example 1 except that the obtained black material was used.
- Example 1 A coating film was prepared in the same manner as in Example 1 except that carbon black was used.
- the present invention it is possible to provide a near-infrared ray transmissive black material which can sufficiently absorb visible light and sufficiently suppress the absorption of near infrared rays.
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Abstract
Description
例えば、特許文献1には、磁性材料と着色顔料とワニスを含む赤外線透過性インキが記載されており、このようなインキは秘匿性に優れるとされている。
しかしながら、特許文献1のインキは、近赤外線の吸収を抑制する効果が不充分であるという問題がある。
このようなカラーフィルターとして、例えば、特許文献2には、ビスベンゾフラノン系顔料等の近赤外透過黒色色材を含有するカラーフィルター用組成物が記載されており、このような組成物は、可視光成分に由来するノイズが少ないとされている。
しかしながら、引用文献2の近赤外透過黒色色材であっても、可視光を吸収する効果が不充分であったり、近赤外線の吸収を充分に抑制できなかったりするという問題がある。
以下、本発明を詳述する。
上記オキサジン樹脂を含有することで、可視光の吸収と近赤外線の吸収抑制とを両立することができる。
芳香族系オキサジン樹脂としては、樹脂の基本構造にベンゼン環を有するベンゾオキサジン樹脂、ナフタレン環を有するナフトオキサジン樹脂等が挙げられる。
なかでも、可視光に対する吸収性が高く、より高い黒色度を示すことからナフトオキサジン樹脂が好ましい。
上記ベンゾオキサジン樹脂は、繰り返し構造中にベンゼン環を複数有するものであってもよい。また、上記ナフトオキサジン樹脂は、繰り返し構造中にナフタレン環を複数有するものであってもよい。
上記オキサジンの構造として、芳香族オキサジンであるベンゾオキサジンの部分構造の一例を下記式(1)に、ナフトキサジンの部分構造の一例を下記式(2)及び(3)に示す。
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
上記アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基等が挙げられる。
上記アルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、t-ブトキシ基等が挙げられる。
上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
上記アルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、t-ブチル基等が挙げられる。
上記アルコキシ基としては、例えば、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、t-ブトキシ基等が挙げられる。
また、上記オキサジン樹脂は、窒素含有量が0.5重量%以上であることが好ましく、1.0重量%以上であることがより好ましく、20.0重量%以下であることが好ましく、10.0重量%以下であることがより好ましい。
上記酸素含有量及び窒素含有量は、例えば、X線光電子分光法により測定することができる。
また、上記オキサジン樹脂における炭素/窒素の重量比は、2.5以上であることが好ましく、5.0以上であることがより好ましく、100.0以下であることが好ましく、50.0以下であることがより好ましい。
上記炭素/酸素の重量比及び炭素/窒素の重量比は、例えば、X線光電子分光法により測定することができる。
また、上記方法において、ジヒドロキシナフタレンに代えて、フェノール類(例えば、フェノール、ビスフェノール等)を用いることで、ベンゾオキサジン樹脂を製造することができる。
また、ホルムアルデヒドには、その重合形態としてパラホルムアルデヒドがあり、こちらの方も原料として使用可能であるが、反応性が劣るため、好ましくは上記したホルマリンが用いられる。
分子量を小さくする方が好ましいので、置換基Rは、メチル基、エチル基、プロピル基等が好ましく、実際の化合物名としては、メチルアミン、エチルアミン、プロピルアミン等が好ましく使用できる。最も好ましいものは、分子量が一番小さなメチルアミンである。
このうち、反応性の高さから、1,5-ジヒドロキシナフタレン、2,6-ジヒドロキシナフタレンが好ましい。更に1,5-ジヒドロキシナフタレンが最も反応性が高いので好ましい。
反応条件によっては、反応中に揮発等により原料を失うので、最適な配合比は正確に上記比率とは限らないが、ジヒドロキシナフタレン1モルに対して、脂肪族アミンを0.8~2.2モル、ホルムアルデヒドを1.6~4.4モルの配合比の範囲で配合することが好ましい。
上記脂肪族アミンを0.8モル以上とすることにより、オキサジン環を十分に形成することができ、重合を好適に進めることができる。また2.2モル以下とすることにより、反応に必要なホルムアルデヒドを余計に消費することがないため、反応が順調に進み、所望のナフトキサジンを得ることができる。
同様に、ホルムアルデヒドを1.6モル以上とすることで、オキサジン環を充分に形成することができ、重合を好適に進めることができる。また4.4モル以下とすることで、副反応の発生を低減できるため好ましい。
上記溶媒としては、例えば、メタノール、エタノール、イソプロパノール等のアルコール類、アセトン、メチルエチルケトン等のケトン類、テトラヒドロフラン、ジオキサン、クロロホルム、酢酸エチル、ジメチルホルムアミド、ジメチルスルホキシド等が挙げられる。
上記SP値が9.0以上の溶媒としては、エタノール(12.7)、メタノール(14.7)、イソプロパノール(11.5)、クレゾール(13.3)、エチレングリコール(14.2)、フェノール(14.5)、水(23.4)、DMF(N,N-ジメチルホルムアミド、12.3)、ジメチルスルホキシド(DMSO、13.0)、メチルエチルケトン(9.3)、ジオキサン(10.3)、酢酸エチル(9.0)、クロロホルム(9.4)、アセトン(10.0)等が挙げられる。
上記SP値が9.0以上の溶媒としては、SP値が9.0~15.0である溶媒がより好ましい。また、上記溶媒を単一成分のみを使う場合は、沸点が50~150℃であることが好ましい。沸点が50~130℃、かつ、SP値が9.0以上である溶媒を含有することが更に好ましい。
上記沸点が150℃以上である溶媒の含有量のより好ましい下限は45体積%である。
上記反応では、加温を続けることで、作製されたオキサジン環が開き、重合が起こると分子量が増加し、いわゆるオキサジン樹脂となる。
また、粒子の作製を均一に行うためには、反応時に粒子が分散された状態が好ましい。分散方法としては、撹拌、超音波、回転等公知の方法が利用できる。また、分散状態を改善するために、適当な分散剤を添加しても良い。
上記オキサジン樹脂を形成する工程は、室温でも反応が徐々に進行するが、反応を効率的に進行させるためには、50~150℃の温度で行うことが好ましい。また、反応時間は、温度によって調整可能であり、通常30分から20時間であることが好ましい。上記条件での反応によって、球状のオキサジン樹脂粒子が得られる。この工程で得られたオキサジン樹脂粒子は、反応条件によって、緑色、茶色、又は黒色を示す。
なお、オキサジン樹脂粒子の粒子径は溶液の濃度、反応温度、原料のモル比及び撹拌条件等のパラメータによって調整することができる。
加熱時の雰囲気は、窒素やアルゴン等の不活性ガス雰囲気が好ましく、また、蒸発を抑えるために密閉された容器で行うことが好ましい。
上記範囲とすることで、可視光を充分に吸収して、高い黒色性を発現させることができる。
上記平均透過率は、15%以下であることがより好ましく、12%以下であることが更に好ましい。
上記平均透過率は、例えば、積分球付きの分光光度計を用いて測定することができる。
上記範囲とすることで、近赤外線の透過性を充分に高めることができる。
上記平均透過率は、70%以上であることがより好ましい。
上記平均透過率は、例えば、積分球付きの分光光度計を用いて測定することができる。
上記範囲とすることで、粒子径の均一性に優れ、溶媒中の分散性が良好な黒色粒子とすることが可能となる。
上記ゼータ電位の好ましい下限は-60mV、好ましい上限は+70mVである。
なお、上記ゼータ電位は、例えば、顕微鏡電気泳動方式ゼータ電位測定装置を用いて、黒色粒子が分散した溶液を測定用セルに注入し、顕微鏡で観察しながら電圧をかけ、粒子が動かなくなった(静止した)時の電位を測定することで求めることができる。
密度が1.80g/cm3以下であることで、高い分散性を得ることができる。上記密度の好ましい下限は1.20g/cm3、好ましい上限は1.70g/cm3である。
体積抵抗率が1.0×107Ω・cm以上であることで、高い絶縁性を確保することができる。より好ましくは1.0×108Ω・cm以上、更に好ましくは1.0×1011Ω・cm以上である。また、好ましい上限は1.0×1018Ω・cmである。
上記のような構造を有することで緻密性の高い粒子を得ることができる。
本願発明において、ベンゼン環に由来する質量スペクトルとは、77.12付近の質量スペクトルをいい、ナフタレン環に由来する質量スペクトルとは、127.27付近の質量スペクトルをいう。
なお、上記測定は、例えば、TOF-SIMS装置(ION-TOF社製)等を用いて行うことができる。
上記範囲とすることで、充分な黒色度と高い分散性を得ることができる。
上記平均粒子径は、0.02μm以上であることがより好ましく、5.0μm以下であることがより好ましい。
上記粒子径のCV値が20%以下であると、黒色材料の単分散性が良くなり、黒色顔料として利用する場合に粒子を最密充填しやすくなる。その結果、可視光に対する遮蔽効果を高めることが可能となる。上記粒子径のCV値のより好ましい上限は15%である。なお、下限については特に限定されないが0.5%が好ましい。
粒子径のCV値(%)とは、標準偏差を平均粒子径で割った値を百分率で表したものであり、下記式により求められる数値のことである。CV値が小さいほど粒子径のばらつきが小さいことを意味する。
粒子径のCV値(%)=(粒子径の標準偏差/平均粒子径)×100
平均粒子径及び標準偏差は、例えば、FE-TEMを用いて測定することができる。
これにより、本発明の効果を高めることができる。
上記平均球形度のより好ましい下限は95%である。
なお、球形度(短径/長径)は、FE-TEM又はFE-SEMを用いて撮影された電子顕微鏡写真を画像解析装置を用いて、解析処理することにより測定することができ、平均球形度は、電子顕微鏡写真中において任意に選ばれた例えば100個の粒子について、球形度の平均値を求めることにより算出することができる。
上記範囲とすることで、高い黒色性を発現させることができる。
上記明度L*は25以下であることがより好ましく、20以下であることが更に好ましい。
上記明度L*は、例えば、JIS Z 8722:2009に準拠して分光測色計により測定することができる。
上記近赤外線透過性インク、近赤外線透過性フィルターもまた本発明の1つである。
1,5-ジヒドロキシナフタレン(1,5-DHN、東京化成社製)1.20gと、1,3,5-トリメチルヘキサヒドロ-1,3,5-トリアジン(東京化成社製)0.98gをエタノール50mlに順次溶解し、エタノール混合溶液を作製した。
次に、得られた混合溶液を80℃で5.0時間加熱撹拌(回転数:300rpm)した。溶液をガラスフィルターで濾過し、エタノールで3回洗浄した後に、50℃で3時間真空乾燥して、更に、200℃で12時間真空加熱することによって、近赤外線透過性黒色材料としてのナフトオキサジン樹脂粒子を得た。
得られた黒色材料4重量部をポリビニルブチラール樹脂40重量部に分散し、スライドガラス上に乾燥後の厚さが30μmとなるように塗工し、100℃で2時間乾燥して塗布膜を得た。
1,5-ジヒドロキシナフタレン(東京化成社製)1.0gと、40%メチルアミン(富士フイルム和光純薬社製)0.5gと、37%ホルムアルデヒド水溶液(富士フイルム和光純薬社製)1.0gとをイソプロパノールと水の混合溶液(イソプロパノールと水の重量比=4:1)500mlに順次溶解した。
次に、得られた混合溶液を30℃で一晩反応させ、更に80℃で10時間加熱撹拌(回転数:300rpm)した。粒子を回収、洗浄し、50℃で3時間真空乾燥して、更に、220℃で20時間熱処理することによって、近赤外線透過性黒色材料としてのナフトオキサジン樹脂粒子を得た。
得られた黒色材料を用いた以外は、実施例1と同様にして塗布膜を作製した。
カーボンブラックを用いた以外は、実施例1と同様にして塗布膜を作製した。
(1)平均粒子径、CV値及び平均球形度
実施例で得られた黒色材料及び比較例で用いたカーボンブラックのFE-SEM像を画像解析ソフト(WINROOF、三谷商事社製)を用いて解析することにより、平均粒子径を測定した。
また、実施例で得られた黒色材料について、標準偏差を算出し、得られた数値から粒子径の変動係数(CV値)を算出した。
更に、実施例で得られた黒色材料について、粒子の最小径と最大径の比から球形度を求め、平均球形度を算出した。
実施例及び比較例で得られた塗布膜について、積分球付き分光光度計(日本分光社製、V-670)を用いて、波長400~800nmの可視光領域及び波長900~2500nmの近赤外領域での反射スペクトルを測定し、それぞれの波長範囲での透過率の幾何平均を求め、それぞれの波長範囲での透過率の平均値として、平均透過率を求めた。
また、実施例及び比較例で得られた塗布膜について、積分球付き分光光度計(日本分光社製、V-670)を用い、JIS Z 8722:2009に準拠してCIE LAB(L*a*b*)表色系における明度L*値を測定した。
Claims (6)
- オキサジン樹脂を含む、近赤外線透過性黒色材料。
- オキサジン樹脂は、ナフトオキサジン樹脂である、請求項1に記載の近赤外線透過性黒色材料。
- 粒子形状であり、平均粒子径が0.02μm以上10.0μm以下である、請求項1又は2に記載の近赤外線透過性黒色材料。
- 波長400~800nmの可視光領域での平均透過率が20%以下であり、かつ、波長900~2500nmの近赤外領域での平均透過率が60%以上である、請求項1~3のいずれかに記載の近赤外線透過性黒色材料。
- 請求項1~4のいずれかに記載の近赤外線透過性黒色材料を含む近赤外線透過性インク。
- 請求項1~4のいずれかに記載の近赤外線透過性黒色材料を含む近赤外線透過性フィルター。
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