JP3150745B2 - Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing them - Google Patents
Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing themInfo
- Publication number
- JP3150745B2 JP3150745B2 JP00032792A JP32792A JP3150745B2 JP 3150745 B2 JP3150745 B2 JP 3150745B2 JP 00032792 A JP00032792 A JP 00032792A JP 32792 A JP32792 A JP 32792A JP 3150745 B2 JP3150745 B2 JP 3150745B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- copper
- weight
- infrared absorbing
- infrared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims description 23
- 239000011358 absorbing material Substances 0.000 title claims description 16
- 239000006096 absorbing agent Substances 0.000 title claims description 9
- 239000005749 Copper compound Substances 0.000 claims description 28
- 150000001880 copper compounds Chemical class 0.000 claims description 28
- 229910019142 PO4 Inorganic materials 0.000 claims description 26
- 239000010452 phosphate Substances 0.000 claims description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 26
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 20
- 150000003556 thioamides Chemical class 0.000 claims description 18
- 150000003585 thioureas Chemical class 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 3
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 3
- 229930002875 chlorophyll Natural products 0.000 claims description 3
- 235000019804 chlorophyll Nutrition 0.000 claims description 3
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229940099898 chlorophyllin Drugs 0.000 claims description 2
- 235000019805 chlorophyllin Nutrition 0.000 claims description 2
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 22
- 239000000463 material Substances 0.000 description 18
- -1 cobalt complex salts Chemical class 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 239000008188 pellet Substances 0.000 description 10
- 238000000411 transmission spectrum Methods 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229920005990 polystyrene resin Polymers 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- HQEMUQNZGCZHHN-UHFFFAOYSA-N (3-nitrophenyl)thiourea Chemical compound NC(=S)NC1=CC=CC([N+]([O-])=O)=C1 HQEMUQNZGCZHHN-UHFFFAOYSA-N 0.000 description 1
- ZJLRWLYVCHKHMM-UHFFFAOYSA-N (4-aminophenyl)thiourea Chemical compound NC(=S)NC1=CC=C(N)C=C1 ZJLRWLYVCHKHMM-UHFFFAOYSA-N 0.000 description 1
- BLYAANPIHFKKMQ-UHFFFAOYSA-N (4-nitrophenyl)thiourea Chemical compound NC(=S)NC1=CC=C([N+]([O-])=O)C=C1 BLYAANPIHFKKMQ-UHFFFAOYSA-N 0.000 description 1
- PXDTZJRKXYJXTL-UHFFFAOYSA-N 1,1-dibenzyl-3-(2-phenylethyl)thiourea Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)NCCC1=CC=CC=C1 PXDTZJRKXYJXTL-UHFFFAOYSA-N 0.000 description 1
- FPZXQVCYHDMIIA-UHFFFAOYSA-N 1,1-diphenylthiourea Chemical compound C=1C=CC=CC=1N(C(=S)N)C1=CC=CC=C1 FPZXQVCYHDMIIA-UHFFFAOYSA-N 0.000 description 1
- FYBHEPNLHXGWJV-UHFFFAOYSA-N 1,3-bis(2-hydroxyethyl)thiourea Chemical compound OCCNC(=S)NCCO FYBHEPNLHXGWJV-UHFFFAOYSA-N 0.000 description 1
- SSTJIFMUJKCEAB-UHFFFAOYSA-N 1,3-di(docosyl)thiourea Chemical compound CCCCCCCCCCCCCCCCCCCCCCNC(=S)NCCCCCCCCCCCCCCCCCCCCCC SSTJIFMUJKCEAB-UHFFFAOYSA-N 0.000 description 1
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- LRDWZYFXZNDIRZ-UHFFFAOYSA-N 1,3-dioctadecylthiourea Chemical compound CCCCCCCCCCCCCCCCCCNC(=S)NCCCCCCCCCCCCCCCCCC LRDWZYFXZNDIRZ-UHFFFAOYSA-N 0.000 description 1
- MFCXZZJQPDIXAS-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-phenylthiourea Chemical compound OCCNC(=S)NC1=CC=CC=C1 MFCXZZJQPDIXAS-UHFFFAOYSA-N 0.000 description 1
- BPFUTHPEILBSRX-UHFFFAOYSA-N 1-(4-aminophenyl)-3-phenylthiourea Chemical compound C1=CC(N)=CC=C1NC(=S)NC1=CC=CC=C1 BPFUTHPEILBSRX-UHFFFAOYSA-N 0.000 description 1
- KJHGRSFROPLPID-UHFFFAOYSA-N 1-(4-bromophenyl)-3-phenylthiourea Chemical compound C1=CC(Br)=CC=C1NC(=S)NC1=CC=CC=C1 KJHGRSFROPLPID-UHFFFAOYSA-N 0.000 description 1
- HNDPPFMCVAHWCO-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-ethylthiourea Chemical compound CCNC(=S)NC1=CC=C(Cl)C=C1 HNDPPFMCVAHWCO-UHFFFAOYSA-N 0.000 description 1
- XYAKDKSYCSTBMN-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-phenylthiourea Chemical compound C1=CC(Cl)=CC=C1NC(=S)NC1=CC=CC=C1 XYAKDKSYCSTBMN-UHFFFAOYSA-N 0.000 description 1
- OYEDAMXEBRVBQC-UHFFFAOYSA-N 1-(4-hydroxyphenyl)-3-methylthiourea Chemical compound CNC(=S)NC1=CC=C(O)C=C1 OYEDAMXEBRVBQC-UHFFFAOYSA-N 0.000 description 1
- PWLPSXPCUHUSAT-UHFFFAOYSA-N 1-(4-hydroxyphenyl)-3-phenylthiourea Chemical compound C1=CC(O)=CC=C1NC(=S)NC1=CC=CC=C1 PWLPSXPCUHUSAT-UHFFFAOYSA-N 0.000 description 1
- JMKRMQGOPWYOGL-UHFFFAOYSA-N 1-(4-methoxyphenyl)-3-phenylthiourea Chemical compound C1=CC(OC)=CC=C1NC(=S)NC1=CC=CC=C1 JMKRMQGOPWYOGL-UHFFFAOYSA-N 0.000 description 1
- NNWRRGBHDKYELI-UHFFFAOYSA-N 1-(4-nitrophenyl)-3-phenylthiourea Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=S)NC1=CC=CC=C1 NNWRRGBHDKYELI-UHFFFAOYSA-N 0.000 description 1
- FXTHEXIBLBGGRA-UHFFFAOYSA-N 1-ethyl-3-(2-hydroxyethyl)thiourea Chemical compound CCNC(=S)NCCO FXTHEXIBLBGGRA-UHFFFAOYSA-N 0.000 description 1
- OROCFDLTBPBLFS-UHFFFAOYSA-N 1-ethyl-3-phenylthiourea Chemical compound CCNC(=S)NC1=CC=CC=C1 OROCFDLTBPBLFS-UHFFFAOYSA-N 0.000 description 1
- YNXICDMQCQPQEW-UHFFFAOYSA-N 1-naphthyl dihydrogen phosphate Chemical compound C1=CC=C2C(OP(O)(=O)O)=CC=CC2=C1 YNXICDMQCQPQEW-UHFFFAOYSA-N 0.000 description 1
- GCZZOZBWAZHCAN-UHFFFAOYSA-N 1-phenyl-3-(1,3-thiazol-2-yl)thiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=NC=CS1 GCZZOZBWAZHCAN-UHFFFAOYSA-N 0.000 description 1
- BLMAZZIHNCRLLZ-UHFFFAOYSA-N 1-phenyl-3-thiophen-2-ylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CS1 BLMAZZIHNCRLLZ-UHFFFAOYSA-N 0.000 description 1
- LJUYKMMIBKJBGH-UHFFFAOYSA-N 18-ethylsulfanyloctadecan-1-amine Chemical compound CCSCCCCCCCCCCCCCCCCCCN LJUYKMMIBKJBGH-UHFFFAOYSA-N 0.000 description 1
- IEPWIPXPWWGAFB-UHFFFAOYSA-N 18-octadecylsulfanyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCCN IEPWIPXPWWGAFB-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- HJCTVUWPHAZTLI-UHFFFAOYSA-N 2-ethylsulfanylethanamine Chemical compound CCSCCN HJCTVUWPHAZTLI-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- XTNIPMWSEHYGST-UHFFFAOYSA-N 22-docosylsulfanyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCCCCCCN XTNIPMWSEHYGST-UHFFFAOYSA-N 0.000 description 1
- XTYCZDGWBVPSRA-UHFFFAOYSA-N 4-chloro-N-ethylsulfanylbenzamide Chemical compound C(C)SNC(C1=CC=C(C=C1)Cl)=O XTYCZDGWBVPSRA-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- XYBHFIJHONARNZ-UHFFFAOYSA-N C(CC)O[Cu]OCCC.C(C)O[Cu]OCC.[Cu] Chemical compound C(CC)O[Cu]OCCC.C(C)O[Cu]OCC.[Cu] XYBHFIJHONARNZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- MCVKWIMLBLTUBL-UHFFFAOYSA-N N-(4-aminophenyl)benzenecarbothioamide Chemical compound NC1=CC=C(C=C1)NC(C1=CC=CC=C1)=S MCVKWIMLBLTUBL-UHFFFAOYSA-N 0.000 description 1
- FYFCFOVWYNRPTO-UHFFFAOYSA-N N-chloro-2-phenylbenzenecarbothioamide Chemical compound ClNC(C1=C(C=CC=C1)C1=CC=CC=C1)=S FYFCFOVWYNRPTO-UHFFFAOYSA-N 0.000 description 1
- IBPQLBFSQQBBIS-UHFFFAOYSA-N N-docosylethanethioamide Chemical compound C(C)(=S)NCCCCCCCCCCCCCCCCCCCCCC IBPQLBFSQQBBIS-UHFFFAOYSA-N 0.000 description 1
- GMEHFXXZSWDEDB-UHFFFAOYSA-N N-ethylthiourea Chemical compound CCNC(N)=S GMEHFXXZSWDEDB-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- QIOZLISABUUKJY-UHFFFAOYSA-N Thiobenzamide Chemical compound NC(=S)C1=CC=CC=C1 QIOZLISABUUKJY-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940067597 azelate Drugs 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- WBZLOKPDCSPGJZ-UHFFFAOYSA-L copper 2-methylbenzoate Chemical compound CC1=C(C(=O)[O-])C=CC=C1.[Cu+2].CC1=C(C(=O)[O-])C=CC=C1 WBZLOKPDCSPGJZ-UHFFFAOYSA-L 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- BNPNTOCOXIIGRH-UHFFFAOYSA-L copper;2,3,4-trichlorobenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C(Cl)C(Cl)=C1Cl.[O-]C(=O)C1=CC=C(Cl)C(Cl)=C1Cl BNPNTOCOXIIGRH-UHFFFAOYSA-L 0.000 description 1
- ZLBNIEALSOKBJD-UHFFFAOYSA-L copper;2,3-dichlorobenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC(Cl)=C1Cl.[O-]C(=O)C1=CC=CC(Cl)=C1Cl ZLBNIEALSOKBJD-UHFFFAOYSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- QPXYRZNGQKQMIE-UHFFFAOYSA-L copper;2,5-dimethylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(C)C(S([O-])(=O)=O)=C1.CC1=CC=C(C)C(S([O-])(=O)=O)=C1 QPXYRZNGQKQMIE-UHFFFAOYSA-L 0.000 description 1
- BOZZLSTZCUGZHL-UHFFFAOYSA-L copper;2-aminobenzoate Chemical compound [Cu+2].NC1=CC=CC=C1C([O-])=O.NC1=CC=CC=C1C([O-])=O BOZZLSTZCUGZHL-UHFFFAOYSA-L 0.000 description 1
- OPEIQWUGFPOGLX-UHFFFAOYSA-L copper;2-benzoylbenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 OPEIQWUGFPOGLX-UHFFFAOYSA-L 0.000 description 1
- RFOBAXICGWDOKB-UHFFFAOYSA-L copper;2-chlorobenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1Cl.[O-]C(=O)C1=CC=CC=C1Cl RFOBAXICGWDOKB-UHFFFAOYSA-L 0.000 description 1
- PLRGOBLMPRZEQF-UHFFFAOYSA-L copper;2-methoxycarbonyl-5-methylbenzenesulfonate Chemical compound [Cu+2].COC(=O)C1=CC=C(C)C=C1S([O-])(=O)=O.COC(=O)C1=CC=C(C)C=C1S([O-])(=O)=O PLRGOBLMPRZEQF-UHFFFAOYSA-L 0.000 description 1
- KOKFUFYHQQCNNJ-UHFFFAOYSA-L copper;2-methylpropanoate Chemical compound [Cu+2].CC(C)C([O-])=O.CC(C)C([O-])=O KOKFUFYHQQCNNJ-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- DRTKWJRLPDAHPN-UHFFFAOYSA-L copper;4-aminobenzoate Chemical compound [Cu+2].NC1=CC=C(C([O-])=O)C=C1.NC1=CC=C(C([O-])=O)C=C1 DRTKWJRLPDAHPN-UHFFFAOYSA-L 0.000 description 1
- KGHTXGGEVNWIMZ-UHFFFAOYSA-L copper;4-bromobenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C(Br)C=C1.[O-]C(=O)C1=CC=C(Br)C=C1 KGHTXGGEVNWIMZ-UHFFFAOYSA-L 0.000 description 1
- QNXVQZCLZLGOEP-UHFFFAOYSA-L copper;4-nitrobenzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C([N+]([O-])=O)C=C1.[O-]C(=O)C1=CC=C([N+]([O-])=O)C=C1 QNXVQZCLZLGOEP-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-UHFFFAOYSA-L 0.000 description 1
- ZZBHLLYRFXFBLC-UHFFFAOYSA-N copper;decanedioic acid Chemical compound [Cu].OC(=O)CCCCCCCCC(O)=O ZZBHLLYRFXFBLC-UHFFFAOYSA-N 0.000 description 1
- OBITVTZBIATBCL-UHFFFAOYSA-L copper;decanoate Chemical compound [Cu+2].CCCCCCCCCC([O-])=O.CCCCCCCCCC([O-])=O OBITVTZBIATBCL-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- NVNJDKNLESDRQF-UHFFFAOYSA-L copper;docosanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O NVNJDKNLESDRQF-UHFFFAOYSA-L 0.000 description 1
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical compound [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 1
- OUNVHRVEZKVXQB-UHFFFAOYSA-N copper;dodecyl benzenesulfonate Chemical compound [Cu].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 OUNVHRVEZKVXQB-UHFFFAOYSA-N 0.000 description 1
- QXPQHPAJDGRSQA-UHFFFAOYSA-L copper;dodecyl sulfate Chemical compound [Cu+2].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O QXPQHPAJDGRSQA-UHFFFAOYSA-L 0.000 description 1
- ZCXLQZOQWCXFNN-UHFFFAOYSA-N copper;hexanedioic acid Chemical compound [Cu].OC(=O)CCCCC(O)=O ZCXLQZOQWCXFNN-UHFFFAOYSA-N 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- CAMXOLUXKJMDSB-UHFFFAOYSA-L copper;naphthalene-1-carboxylate Chemical compound [Cu+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 CAMXOLUXKJMDSB-UHFFFAOYSA-L 0.000 description 1
- UFXHHGSBXSVQCB-UHFFFAOYSA-L copper;naphthalene-1-sulfonate Chemical compound [Cu+2].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 UFXHHGSBXSVQCB-UHFFFAOYSA-L 0.000 description 1
- HHVMSVSAWRRCIK-UHFFFAOYSA-N copper;octanedioic acid Chemical compound [Cu].OC(=O)CCCCCCC(O)=O HHVMSVSAWRRCIK-UHFFFAOYSA-N 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- LMCVMQNMDSVUFJ-UHFFFAOYSA-N copper;pentanedioic acid Chemical compound [Cu].OC(=O)CCCC(O)=O LMCVMQNMDSVUFJ-UHFFFAOYSA-N 0.000 description 1
- NBPFTDFXKORRKN-UHFFFAOYSA-L copper;pentanoate Chemical compound [Cu+2].CCCCC([O-])=O.CCCCC([O-])=O NBPFTDFXKORRKN-UHFFFAOYSA-L 0.000 description 1
- GSCLWPQCXDSGBU-UHFFFAOYSA-L copper;phthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O GSCLWPQCXDSGBU-UHFFFAOYSA-L 0.000 description 1
- PJBGIAVUDLSOKX-UHFFFAOYSA-N copper;propanedioic acid Chemical compound [Cu].OC(=O)CC(O)=O PJBGIAVUDLSOKX-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- HWDGVJUIHRPKFR-UHFFFAOYSA-I copper;trisodium;18-(2-carboxylatoethyl)-20-(carboxylatomethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18-dihydroporphyrin-21,23-diide-2-carboxylate Chemical compound [Na+].[Na+].[Na+].[Cu+2].N1=C(C(CC([O-])=O)=C2C(C(C)C(C=C3C(=C(C=C)C(=C4)[N-]3)C)=N2)CCC([O-])=O)C(=C([O-])[O-])C(C)=C1C=C1C(CC)=C(C)C4=N1 HWDGVJUIHRPKFR-UHFFFAOYSA-I 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- AMZMQXJQIYKBJU-UHFFFAOYSA-N iodo benzoate Chemical compound IOC(=O)C1=CC=CC=C1 AMZMQXJQIYKBJU-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- ZAGSPKBXULZTTL-UHFFFAOYSA-N n-(3-chlorophenyl)benzenecarbothioamide Chemical compound ClC1=CC=CC(NC(=S)C=2C=CC=CC=2)=C1 ZAGSPKBXULZTTL-UHFFFAOYSA-N 0.000 description 1
- MGLHJRBKHQHAMT-UHFFFAOYSA-N n-(4-nitrophenyl)benzenecarbothioamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=S)C1=CC=CC=C1 MGLHJRBKHQHAMT-UHFFFAOYSA-N 0.000 description 1
- KQJYDHWNYPRIRY-UHFFFAOYSA-N n-cyclohexylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC1CCCCC1 KQJYDHWNYPRIRY-UHFFFAOYSA-N 0.000 description 1
- VXQROEXTWNTASQ-UHFFFAOYSA-N n-methylbenzenecarbothioamide Chemical compound CNC(=S)C1=CC=CC=C1 VXQROEXTWNTASQ-UHFFFAOYSA-N 0.000 description 1
- BNLLHLUAOXAUNQ-UHFFFAOYSA-N n-methylethanethioamide Chemical compound CNC(C)=S BNLLHLUAOXAUNQ-UHFFFAOYSA-N 0.000 description 1
- QBSWTIGUPBSBDE-UHFFFAOYSA-N n-octadecylbenzenecarbothioamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=S)C1=CC=CC=C1 QBSWTIGUPBSBDE-UHFFFAOYSA-N 0.000 description 1
- BOQKCADLPNLYCZ-UHFFFAOYSA-N n-phenylbenzenecarbothioamide Chemical compound C=1C=CC=CC=1C(=S)NC1=CC=CC=C1 BOQKCADLPNLYCZ-UHFFFAOYSA-N 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- ULZQMOTWAKBBPV-UHFFFAOYSA-N n-propylbenzenecarbothioamide Chemical compound CCCNC(=S)C1=CC=CC=C1 ULZQMOTWAKBBPV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- XQWBMZWDJAZPPX-UHFFFAOYSA-N pyridine-3-carbothioamide Chemical compound NC(=S)C1=CC=CN=C1 XQWBMZWDJAZPPX-UHFFFAOYSA-N 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940079841 sodium copper chlorophyllin Drugs 0.000 description 1
- 235000013758 sodium copper chlorophyllin Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Optical Record Carriers And Manufacture Thereof (AREA)
- Optical Filters (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は銅化合物とチオ尿素系誘
導体又はチオアミド系誘導体及び六塩化タングステンと
トリアルキル又はトリアリールフォスフェートとから成
る近赤外線吸収剤用組成物並びに近赤外線吸収材料及び
それらを含有した成形体に関するものである。近赤外線
吸収材料は、最近特に研究開発が盛んに行われている機
能材料であり、近赤外領域の波長を有する半導体レーザ
ー光等を光源とする感光材料、光ディスク用記録材料等
の情報記録材料、赤外線カットフィルターやフィルム等
の光学材料、熱線吸収性グレージング材料として利用す
ることができる。The present invention relates to a composition for a near-infrared ray absorbent comprising a copper compound, a thiourea derivative or a thioamide derivative, tungsten hexachloride and a trialkyl or triaryl phosphate, and a near-infrared ray absorbing material. The present invention relates to a molded article containing: The near-infrared absorbing material is a functional material that has been actively researched and developed recently, and is a photosensitive material using a semiconductor laser beam having a wavelength in the near-infrared region as a light source, and an information recording material such as a recording material for an optical disc. And optical materials such as infrared cut filters and films, and heat ray absorbing glazing materials.
【0002】[0002]
【従来の技術】これまでに開発された近赤外線吸収材料
としては、特公昭60−42269 号公報にはクロム、コバル
ト錯塩、特公昭60−21294 号公報にはチオールニッケル
錯体、特開昭61−115958号公報にはアントラキノン誘導
体、及び特開昭61−218551号公報には700 〜800nm の領
域に極大吸収波長のある新規スクアリリウム化合物が開
示されている。又米国特許第3692688 号に示されるよう
に六塩化タングステン (WCl6) と塩化スズ(SnCl2・2H
2O) をメタクリル酸メチルシラップ(モノマー)に溶解
し、重合して得られる実質的にヘイズのない近赤外線吸
収能に優れた材料が知られている。2. Description of the Related Art The near-infrared absorbing materials developed so far include chromium and cobalt complex salts in Japanese Patent Publication No. Sho 60-42269, thiol nickel complex in Japanese Patent Publication No. Sho 60-21294, and Japanese Patent No. 115958 discloses an anthraquinone derivative, and Japanese Patent Application Laid-Open No. 61-218551 discloses a novel squarylium compound having a maximum absorption wavelength in a range of 700 to 800 nm. Also as shown in U.S. Pat. No. 3692688 tungsten hexachloride (WCl 6) and tin chloride (SnCl 2 · 2H
The 2 O) was dissolved in methyl methacrylate syrup (monomer), substantially material excellent near-infrared absorptivity without haze obtained by polymerization are known.
【0003】[0003]
【発明が解決しようとする課題】従来の近赤外線吸収材
料は、有機系のものは耐久性が悪く環境条件の変化や時
間の経過に伴って初期の能力が劣化してくるという問題
点があり、一方錯体系のものは耐久性があるが、近赤外
部のみならず可視部にも吸収があり、化合物そのものが
強く着色しているものが多く用途が制限されてしまうと
いった問題があった。更にどちらの系のものも特定の波
長において吸収ピークがみられ、そのピークからはずれ
た波長では殆ど吸収能はないものであった。これらの素
材を利用して、例えば近赤外部の波長を有するレーザー
光を光源とする記録体を考えると、レーザー線の波長と
材料の吸収ピークでの波長を合わせる必要がある。しか
し、レーザー線の波長も近赤外線吸収材料の吸収波長も
限られたものしか得られないから、レーザー線の波長と
近赤外線吸収材料の吸収ピークでの波長が合致する組み
合わせは極く限られたものにならざるを得なかった。The conventional near-infrared absorbing material has a problem in that the organic material is poor in durability and its initial performance is deteriorated with changes in environmental conditions and with the passage of time. On the other hand, although the complex type is durable, it has an absorption not only in the near-infrared region but also in the visible region, and there is a problem that the compound itself is strongly colored and its use is often limited. Furthermore, in both systems, an absorption peak was observed at a specific wavelength, and there was almost no absorption ability at a wavelength deviated from the peak. In the case of a recording medium using these materials as a light source, for example, a laser beam having a wavelength in the near infrared region, it is necessary to match the wavelength of the laser beam with the wavelength at the absorption peak of the material. However, since only the wavelength of the laser beam and the absorption wavelength of the near-infrared absorbing material can be obtained, the combinations in which the wavelength of the laser beam and the wavelength at the absorption peak of the near-infrared absorbing material match are extremely limited. I had to become something.
【0004】また、上記従来技術のWCl6と SnCl2・2H2O
をメタクリル酸メチルシラップに溶解した組成物は濃青
色に発色し、近赤外線を良く吸収する性質を持っている
が、暗所で長期間放置の間に褪色するという問題点を有
してた。このように緩やかに進行するフォトクロミズム
などは一定の品質を備えた光学フィルターや熱線吸収性
グレージングなどの工業製品を提供する上で好ましくな
い問題点であった。In addition, the above-mentioned prior art WCl 6 and SnCl 2 .2H 2 O
Is dissolved in methyl methacrylate to develop a deep blue color and has a property of absorbing near-infrared rays well, but has a problem of fading during long-term storage in a dark place. Such a slow progress of photochromism is an unfavorable problem in providing industrial products such as optical filters and heat ray absorbing glazing having a certain quality.
【0005】[0005]
【課題を解決するための手段】本発明は、 800〜2000nm
の近赤外領域全体に一様に吸収がみられ、着色が少なく
且つ耐久性が優れた近赤外線吸収材料について鋭意検討
を重ねた結果、銅化合物とチオ尿素系誘導体又はチオア
ミド系誘導体及び六塩化タングステンとトリアルキル又
はトリアリールフォスフェートから成る組成物を作製す
ることによって、目的とする優れた近赤外線吸収材料が
得られることを見出し、本発明を完成するに至ったもの
である。According to the present invention, there is provided a semiconductor device comprising:
As a result of intensive studies on a near-infrared absorbing material which is uniformly absorbed in the entire near-infrared region, has low coloring and is excellent in durability, a copper compound and a thiourea-based or thioamide-based derivative and hexachloride The present inventors have found that a desired excellent near-infrared absorbing material can be obtained by preparing a composition comprising tungsten and a trialkyl or triaryl phosphate, thereby completing the present invention.
【0006】即ち本発明は、(A) 一般式(I) (R−X)nCu (I) 〔式中、R は水素、アルキル基、シクロアルキル基、ア
リール基、アラルキル基及び複素環残基(各基は1個以
上の置換基を有していても良い)から成る群から選ばれ
る一価基,X は−COO,−SO4,−SO3,−PO4,−O 、n は1
〜4の整数〕で表わされる銅化合物、或はクロロフィル
銅、銅クロロフィリンナトリウム及びビスアセチルアセ
トナート銅より成る群から選ばれる少なくとも一種の銅
化合物1重量部に対して下記一般式(II)Thus, the present invention provides, (A) the general formula (I) in (R-X) n Cu ( I) [wherein, R represents hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the heterocyclic residue monovalent radical selected from the group consisting of group (each group may have one or more substituents), X is -COO, -SO 4, -SO 3, -PO 4, -O, n Is 1
Or an integer of 4 to 1 part by weight of at least one copper compound selected from the group consisting of copper chlorophyll, copper copper chlorophyllin and copper bisacetylacetonate.
【0007】[0007]
【化3】 Embedded image
【0008】(R1, R2,R3は、水素、アルキル基、シク
ロアルキル基、アリール基、アラルキル基及び5員又は
6員の複素環残基から成る群から選ばれる一価基を表わ
し、各基は1個以上の置換基を有していても良く、R1と
R2又はR2とR3は連結して環を形成しても良い) で示され
るチオ尿素誘導体から選ばれる少なくとも一種0.05〜50
重量部から成る成分又は下記一般式(III)(R 1 , R 2 , and R 3 each represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a 5- or 6-membered heterocyclic residue. And each group may have one or more substituents, and R 1 and
R 2 or R 2 and R 3 may be linked to form a ring) at least one selected from thiourea derivatives represented by 0.05 to 50
Component consisting of parts by weight or the following general formula (III)
【0009】[0009]
【化4】 Embedded image
【0010】(R4, R5は、水素、アルキル基、アルケニ
ル基、シクロアルキル基、アリール基、アラルキル基及
び5員又は6員の複素環残基から成る群から選ばれる一
価基を表わし、R5は更にアルコキシ基をも表わし、各基
は1個以上の置換基を有していても良く、R4とR5は連結
して環を形成しても良い) で示されるチオアミド誘導体
から選ばれる少なくとも1種のチオアミド誘導体0.05〜
50重量部から成る成分20〜80重量%と、 (B) 六塩化タングステン1重量部に対してトリアルキル
又はトリアリールフォスフェート0.05〜10重量部から成
る成分80〜20重量%とから成り、(A) +(B) = 100重量
%である近赤外線吸収剤用組成物並びに近赤外線吸収材
料及びそれらを含有した成形体に関する。(R 4 and R 5 represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group and a 5- or 6-membered heterocyclic residue. , R 5 further represents an alkoxy group, each group may have one or more substituents, and R 4 and R 5 may be linked to form a ring). At least one thioamide derivative selected from 0.05 to
(B) 80 to 20% by weight of a component consisting of 0.05 to 10 parts by weight of trialkyl or triaryl phosphate per 1 part by weight of tungsten hexachloride, The present invention relates to a composition for a near-infrared ray absorbing agent wherein A) + (B) = 100% by weight, a near-infrared ray absorbing material, and a molded article containing them.
【0011】本発明で使用する上記の一般式(I)で示
される銅化合物として、下記のものを例示できるが、こ
れらに限定されるものではない。ステアリン酸銅、パナ
ミチン酸銅、オレイン酸銅、ベヘン酸銅、ラウリル酸
銅、カプリン酸銅、カプロン酸銅、吉草酸銅、イソ酪酸
銅、酪酸銅、プロピオン酸銅、酢酸銅、ギ酸銅、水酸化
銅、安息香酸銅、オルトトルイル酸銅、メタトルイル酸
銅、パラトルイル酸銅、パラターシャリブチル安息香酸
銅、オルトクロル安息香酸銅、ジクロル安息香酸銅、ト
リクロル安息香酸銅、p−ブロム安息香酸銅、p−ヨー
ド安息香酸銅、o−ベンゾイル安息香酸銅、p−ニトロ
安息香酸銅、アントラニル酸銅、p−アミノ安息香酸
銅、シュウ酸銅、マロン酸銅、コハク酸銅、グルタル酸
銅、アジピン酸銅、ピメリン酸銅、スベリン酸銅、アゼ
ライン酸銅、セバシン酸銅、フタル酸銅、モノエステル
フタル酸銅、ナフテン酸銅、ナフタリンカルボン酸銅、
酒石酸銅、ジフェニルアミン−2−カルボン酸銅、4−
シクロヘキシル酪酸銅、ジエチルジチオカルバミン酸
銅、グルコン酸銅、ジエトキシ銅、ジ−i−プロポキシ
銅、オクチル酸銅、アルキルベンゼンスルホン酸銅、p
−トルエンスルホン酸銅、ナフタリンスルホン酸銅、ナ
フチルアミンスルホン酸銅、n−ドデシルベンゼンスル
ホン酸銅、ドデシル硫酸銅、2,5 −ジメチルベンゼンス
ルホン酸銅、2−カルボメトキシ−5−メチルベンゼン
スルホン酸銅、α−ナフチルリン酸銅、ジ−2−エチル
ヘキシルリン酸銅、イソデシルリン酸銅。Examples of the copper compound represented by the above general formula (I) used in the present invention include, but are not limited to, the following. Copper stearate, copper panaminate, copper oleate, copper behenate, copper laurate, copper caprate, copper caproate, copper valerate, copper isobutyrate, copper butyrate, copper propionate, copper acetate, copper formate, water Copper oxide, copper benzoate, copper orthotoluate, copper metatoluate, copper paratoluate, copper p-tert-butyl benzoate, copper orthochlorobenzoate, copper dichlorobenzoate, copper trichlorobenzoate, copper p-bromobenzoate, p -Copper iodobenzoate, copper o-benzoylbenzoate, copper p-nitrobenzoate, copper anthranilate, copper p-aminobenzoate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate , Copper pimerate, copper suberate, copper azelate, copper sebacate, copper phthalate, copper monoester phthalate, copper naphthenate, copper naphthalenecarboxylate,
Copper tartrate, copper diphenylamine-2-carboxylate, 4-
Copper cyclohexyl butyrate, copper diethyldithiocarbamate, copper gluconate, copper diethoxy, copper di-i-propoxy, copper octylate, copper alkylbenzenesulfonate, p
-Copper toluenesulfonate, copper naphthalenesulfonate, copper naphthylaminesulfonate, copper n-dodecylbenzenesulfonate, copper dodecylsulfate, copper 2,5-dimethylbenzenesulfonate, copper 2-carbomethoxy-5-methylbenzenesulfonate , Copper α-naphthyl phosphate, copper di-2-ethylhexyl phosphate, copper isodecyl phosphate.
【0012】本発明で使用する一般式(II)で示される
チオ尿素誘導体として以下のものを例示できるが、これ
らに限定されるものではない。1−エチル−3−フェニ
ルチオウレア、1,3 −ジフェニルチオウレア、1,3 −ジ
エチルチオウレア、1−エチル−3− p−クロロフェニ
ルチオウレア、1−エチル−3−(2−ヒドロキシエチ
ル)チオウレア、1−(2−チアゾリル)−3−フェニ
ルチオウレア、1,3 −ジステアリルチオウレア、1,3 −
ジベヘニルチオウレア、1−エチルチオウレア、1− p
−ブロモフェニル−3−フェニルチオウレア、1−(2
−チオフェニル)−3−フェニルチオウレア、1,3 −ビ
ス(2−ヒドロキシエチル)チオウレア、1−p−アミ
ノフェニル−3−フェニルチオウレア、1−p−ニトロ
フェニル−3−フェニルチオウレア、1−p−ヒドロキ
シフェニル−3−フェニルチオウレア、1,3 −ジ− m−
クロルフェニルチオウレア、エチレンチオウレア、チオ
ウレア、1−メチル−3− p−ヒドロキシフェニルチオ
ウレア、1−フェニルチオウレア、1− m−ニトロフェ
ニルチオウレア、1− p−ニトロフェニルチオウレア、
1− p−アミノフェニルチオウレア、1,3 −ジメチルチ
オウレア、1,3 −ジシクロヘキシルチオウレア、1−フ
ェニル−3−p−クロロフェニルチオウレア、1−フェ
ニル−3− p−メトキシフェニルチオウレア、1,1 −ジ
フェニルチオウレア、1,1 −ジベンジル−3−フェネチ
ルチオウレア、1−フェニル−3−(2−ヒドロキシエ
チル)チオウレア。The thiourea derivative represented by the general formula (II) used in the present invention can be exemplified by the following, but is not limited thereto. 1-ethyl-3-phenylthiourea, 1,3-diphenylthiourea, 1,3-diethylthiourea, 1-ethyl-3-p-chlorophenylthiourea, 1-ethyl-3- (2-hydroxyethyl) thiourea, 1- (2-thiazolyl) -3-phenylthiourea, 1,3-distearylthiourea, 1,3-
Dibehenylthiourea, 1-ethylthiourea, 1-p
-Bromophenyl-3-phenylthiourea, 1- (2
-Thiophenyl) -3-phenylthiourea, 1,3-bis (2-hydroxyethyl) thiourea, 1-p-aminophenyl-3-phenylthiourea, 1-p-nitrophenyl-3-phenylthiourea, 1-p- Hydroxyphenyl-3-phenylthiourea, 1,3-di-m-
Chlorophenylthiourea, ethylenethiourea, thiourea, 1-methyl-3-p-hydroxyphenylthiourea, 1-phenylthiourea, 1-m-nitrophenylthiourea, 1-p-nitrophenylthiourea,
1-p-aminophenylthiourea, 1,3-dimethylthiourea, 1,3-dicyclohexylthiourea, 1-phenyl-3-p-chlorophenylthiourea, 1-phenyl-3-p-methoxyphenylthiourea, 1,1-diphenyl Thiourea, 1,1-dibenzyl-3-phenethylthiourea, 1-phenyl-3- (2-hydroxyethyl) thiourea.
【0013】本発明で使用する一般式(III)で示される
チオアミド誘導体として以下のものを例示できるが、こ
れらに限定されるものではない。N−メチルチオベンツ
アミド、 N−フェニルチオベンツアミド、 N−エチルチ
オエチルアミド、 N−エチルチオ− p−クロルベンツア
ミド、 N−プロピルチオベンツアミド、 N−エチルチオ
ステアリルアミド、 N−1−(2−チアゾリル)チオベ
ンツアミド、 N−ステアリルチオステアリルアミド、 N
−ベヘニルチオベヘニルアミド、チオアセトアミド、 N
−フェニル−チオ− p−ブロモベンツアミド、 N−1−
(2−チオフェニル)チオベンツアミド、 N−ベヘニル
チオアセトアミド、 N− p−アミノフェニルチオベンツ
アミド、 N− p−ニトロフェニルチオベンツアミド、 N
− p−ヒドロキシフェニルチオベンツアミド、 N− m−
クロルフェニルチオベンツアミド、チオニコチン酸アミ
ド、チオアセトアニリド、 O−エチル− N−フェニル
(チオカルバマート)、チオベンツアミド、チオ− m−
ニトロベンツアミド、チオ− p−ニトロベンツアミド、
チオ− p−アミノベンツアミド、 N−メチルチオアセト
アミド、 N−シクロヘキシルベンツアミド、 N−クロロ
フェニルチオベンツアミド、 N− p−メトキシフェニル
チオベンツアミド、 N−ステアリルチオベンツアミド。The thioamide derivative represented by the general formula (III) used in the present invention can be exemplified by the following, but is not limited thereto. N-methylthiobenzamide, N-phenylthiobenzamide, N-ethylthioethylamide, N-ethylthio-p-chlorobenzamide, N-propylthiobenzamide, N-ethylthiostearylamide, N-1- (2 -Thiazolyl) thiobenzamide, N-stearylthiostearylamide, N
-Behenylthiobehenylamide, thioacetamide, N
-Phenyl-thio-p-bromobenzamide, N-1-
(2-thiophenyl) thiobenzamide, N-behenylthioacetamide, N-p-aminophenylthiobenzamide, N-p-nitrophenylthiobenzamide, N
-P-hydroxyphenylthiobenzamide, N-m-
Chlorophenylthiobenzamide, thionicotinamide, thioacetanilide, O-ethyl-N-phenyl (thiocarbamate), thiobenzamide, thio-m-
Nitrobenzamide, thio-p-nitrobenzamide,
Thio-p-aminobenzamide, N-methylthioacetamide, N-cyclohexylbenzamide, N-chlorophenylthiobenzamide, Np-methoxyphenylthiobenzamide, N-stearylthiobenzamide.
【0014】又、本発明で使用するトリアルキル又はト
リアリールフォスフェートとしては、下記のものを例示
できるが、これらに限定されるものではない。トリメチ
ルフォスフェート、トリエチルフォスフェート、トリブ
チルフォスフェート、トリ− 2−エチルヘキシルフォス
フェート、トリブトキシエチルフォスフェート、トリオ
レイルフォスフェート、トリフェニルフォスフェート、
トリクレジルフォスフェート、トリキシレニルフォスフ
ェート、クレジルジフェニルフォスフェート、キシレニ
ルジフェニルフォスフェート、 2−エチルヘキシルジフ
ェニルフォスフェート。The trialkyl or triaryl phosphate used in the present invention can be exemplified by the following, but is not limited thereto. Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate,
Tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate.
【0015】本発明において用いられる銅化合物とチオ
尿素誘導体又はチオアミド誘導体及び六塩化タングステ
ンとトリアルキル又はトリアリールフォスフェートは、
近赤外線吸収性の設定によって含有させる添加量、種類
と比率、加熱温度、加熱時間を変化させることができ
る。銅化合物1重量部に対してチオ尿素誘導体の添加量
は、0.05〜50重量部である。また、銅化合物1重量部に
対してチオアミド誘導体の添加量は、0.05〜50重量部、
好ましくは0.05〜30重量部である。また、六塩化タング
ステンの1重量部に対してトリアルキル又はトリアリー
ルフォスフェートの添加量は、0.05〜10重量部、好まし
くは0.05〜8重量部である。又、(A) 成分は、20〜80重
量%、好ましくは40〜60重量%である。又、同じ含有量
でも透過率は、本発明で得られる樹脂材料が例えば板で
ある時、その板厚によって変化するので、最終的には設
定した板厚における透過率が得られる様に含有量を決定
する必要がある。The copper compound and thiourea derivative or thioamide derivative and tungsten hexachloride and trialkyl or triaryl phosphate used in the present invention are:
The addition amount, type and ratio, heating temperature, and heating time can be changed by setting the near-infrared absorption. The addition amount of the thiourea derivative is 0.05 to 50 parts by weight based on 1 part by weight of the copper compound. Further, the addition amount of the thioamide derivative is 0.05 to 50 parts by weight per 1 part by weight of the copper compound,
Preferably it is 0.05 to 30 parts by weight. Further, the addition amount of the trialkyl or triaryl phosphate is 0.05 to 10 parts by weight, preferably 0.05 to 8 parts by weight based on 1 part by weight of tungsten hexachloride. The component (A) is contained in an amount of 20 to 80% by weight, preferably 40 to 60% by weight. Further, even when the content is the same, the transmittance varies depending on the thickness of the resin material obtained in the present invention, for example, when the resin material is a plate, so that the transmittance is finally obtained at the set thickness. Need to decide.
【0016】本発明において銅化合物1重量部に対して
チオ尿素誘導体又はチオアミド誘導体の添加量が、それ
ぞれ0.05重量部未満の場合、及び六塩化タングステンの
1重量部に対してトリアルキル又はトリアリールフォス
フェートの添加量が0.05重量部未満の場合には、近赤外
線吸収能の向上が十分でない。一方銅化合物1重量部に
対してチオ尿素誘導体又はチオアミド誘導体の添加量が
5重量部を超える場合及び六塩化タングステンの1重量
部に対してトリアルキル又はトリアリールフォスフェー
トの添加量が50重量部を超える場合には、近赤外線吸収
能の向上が見られず、材料中にヘイズが発生する恐れが
ある。又、(A) 成分が20重量%未満、(B) 成分が20重量
%未満には、 800〜2000nmの近赤外領域全体に一様に吸
収がみられない。銅化合物とチオ尿素誘導体又はチオア
ミド誘導体及び六塩化タングステンとトリアルキル又は
トリアリールフォスフェートは、配合比に従ってこのま
ま混合しても良く、バインダー、熱可塑性樹脂粉末等と
共に混合し、更に必要に応じて一般に使用されている添
加剤、例えば難燃剤、熱安定剤、抗酸化剤、光安定剤、
紫外線吸収剤、滑剤、着色剤を加えて配合した組成物と
することもできる。In the present invention, the addition amount of the thiourea derivative or the thioamide derivative is less than 0.05 part by weight with respect to 1 part by weight of the copper compound, and trialkyl or triarylphosphone is added to 1 part by weight of tungsten hexachloride. When the addition amount of the fate is less than 0.05 part by weight, the improvement of the near-infrared absorbing ability is not sufficient. On the other hand, when the added amount of the thiourea derivative or the thioamide derivative exceeds 5 parts by weight with respect to 1 part by weight of the copper compound, and when the added amount of the trialkyl or triaryl phosphate is 50 parts by weight with respect to 1 part by weight of tungsten hexachloride. When the ratio exceeds the above range, no improvement in near-infrared absorbing power is observed, and haze may be generated in the material. When the component (A) is less than 20% by weight and the component (B) is less than 20% by weight, absorption is not uniformly observed over the entire near infrared region of 800 to 2000 nm. The copper compound and the thiourea derivative or the thioamide derivative and the tungsten hexachloride and the trialkyl or triaryl phosphate may be mixed as they are according to the mixing ratio, and may be mixed with a binder, a thermoplastic resin powder, and the like, and further, if necessary, generally. Additives used, such as flame retardants, heat stabilizers, antioxidants, light stabilizers,
A composition may be prepared by adding an ultraviolet absorber, a lubricant, and a coloring agent.
【0017】又、適当な溶媒若しくは分散媒中に混合溶
解若しくは分散するか、バインダーや着色剤等を溶解し
た媒体中に混合分散して組成物としても良い。混合の程
度及び成形体への添加量或は他の物質との配合量は、加
熱処理を行った時、銅化合物とチオ尿素誘導体又はチオ
アミド誘導体及び六塩化タングステンとトリアルキル又
はトリアリールフォスフェート同志が固体のまま或はど
ちらか一方又は両方が溶解して互いに十分接触し得る状
態になる程度になされていれば良いのである。The composition may be mixed and dissolved or dispersed in an appropriate solvent or dispersion medium, or mixed and dispersed in a medium in which a binder, a coloring agent, and the like are dissolved. The degree of mixing and the amount to be added to the molded body or the amount to be blended with other substances are determined by heat treatment when copper compound and thiourea derivative or thioamide derivative, tungsten hexachloride and trialkyl or triaryl phosphate are combined. It is only necessary that the compound be in a solid state or in such a state that one or both of them are dissolved to be in a state where they can sufficiently contact each other.
【0018】本発明における銅化合物とチオ尿素誘導体
又はチオアミド誘導体及び六塩化タングステンとトリア
ルキル又はトリアリールフォスフェートとを含有する組
成物、或はこの組成物を加熱処理して得られる近赤外線
吸収材料を成形体に含有させる方法としては、特別な手
段、混合順序を要することなく、汎用の混合装置、例え
ば熱ロール、バンバリーミキサー又は押出機により成型
するか、それぞれを分散させたスラリーを成形体に噴
霧、塗工、印刷等により塗布或は含浸させれば良い。成
形体は、パルプ、繊維、熱可塑性樹脂、セラミックス等
を抄く、織る、加熱成型する等公知の材料と方法でフィ
ルム、シート或は棒状のものとし、必要に応じて二次加
工して作製する。A composition containing a copper compound and a thiourea derivative or a thioamide derivative and tungsten hexachloride and a trialkyl or triaryl phosphate according to the present invention, or a near-infrared absorbing material obtained by heat-treating this composition As a method of including in the molded body, a special means, without requiring a mixing order, a general-purpose mixing device, such as a hot roll, a Banbury mixer or an extruder, or a slurry in which each is dispersed is formed into a molded body. What is necessary is just to apply or impregnate by spraying, coating, printing, etc. The molded body is made into a film, sheet or rod by known materials and methods such as pulp, fiber, thermoplastic resin, ceramics, etc. I do.
【0019】加熱処理方法は、銅化合物とチオ尿素誘導
体又はチオアミド誘導体及び六塩化タングステンとトリ
アルキル又はトリアリールフォスフェートが反応して近
赤外線吸収能が得られる熱エネルギーが付加できるもの
であれば特に制限はなく、例えば電気ヒーター、赤外線
ランプ、フィルム等溶融成形を挙げることができる。加
熱温度は、一般に40〜400 ℃、好ましくは50〜350 ℃の
範囲内である。加熱時間は、一般に数ミリ秒〜数十分の
範囲内である。又、攪拌、回転、振動を加えて、物質相
互の接触頻度を挙げ、熱エネルギーの伝達を均一にして
反応を速めると共に混合状態を均一化することは好まし
い方法である。The heat treatment method is particularly applicable as long as the copper compound can react with a thiourea derivative or a thioamide derivative and tungsten hexachloride with a trialkyl or triaryl phosphate to add thermal energy capable of obtaining near-infrared absorption. There is no limitation, and examples thereof include melt molding such as an electric heater, an infrared lamp, and a film. The heating temperature is generally in the range of 40-400 ° C, preferably 50-350 ° C. The heating time is generally in the range of several milliseconds to tens of minutes. Further, it is a preferable method to increase the frequency of contact between substances by applying agitation, rotation, and vibration, to make the transfer of heat energy uniform, to speed up the reaction, and to make the mixing state uniform.
【0020】[0020]
【作用】上記の如く、一般式(I)の銅化合物或はクロ
ロフィル銅、銅クロロフィリンナトリウム、ビスアセチ
ルアセトナート銅と、一般式(II)のチオ尿素誘導体又
は一般式(III)のチオアミド誘導体及び六塩化タングス
テンとトリアルキル又はトリアリールフォスフェートと
を含有した混合物を、上記混合方法により加熱混練する
ことによって 800〜2000nmの全域に渡りほぼ一様に近赤
外線を吸収するようになる。その理由は明らかでない
が、以下に示す実施例及び比較例から明らかな様に、チ
オ尿素誘導体、チオアミド誘導体、銅化合物、六塩化タ
ングステン或はトリアルキル又はトリアリールフォスフ
ェートを、それぞれ単独で上記混合方法により加熱混練
しても 800〜2000nmの近赤外領域全域に渡りほぼ一様に
且つ強度に近赤外線を吸収することはなく、単にチオ尿
素誘導体、チオアミド誘導体、銅化合物、六塩化タング
ステンとトリアルキル又はトリアリールフォスフェート
を混合しただけでも同様であることからすれば、チオ尿
素誘導体又はチオアミド誘導体と銅化合物及び六塩化タ
ングステンとトリアルキル又はトリアリールフォスフェ
ートを含有した混合物を、上記混合方法により加熱混練
することにより、チオ尿素誘導体又はチオアミド誘導
体、銅化合物、六塩化タングステンとトリアルキル又は
トリアリールフォスフェートとの間で何らかの反応が起
き、コンプレックス(錯体)が生じていることによると
推定される。As described above, a copper compound of the general formula (I) or copper chlorophyll, sodium copper chlorophyllin, copper bisacetylacetonate, a thiourea derivative of the general formula (II) or a thioamide derivative of the general formula (III) and By heating and kneading a mixture containing tungsten hexachloride and a trialkyl or triaryl phosphate by the above-mentioned mixing method, near infrared rays can be almost uniformly absorbed over the entire range of 800 to 2000 nm. Although the reason is not clear, as is clear from the following Examples and Comparative Examples, a thiourea derivative, a thioamide derivative, a copper compound, tungsten hexachloride, or a trialkyl or triaryl phosphate is mixed alone as described above. Even if it is heated and kneaded by the method, it does not absorb the near-infrared light almost uniformly and intensely over the entire near-infrared region of 800 to 2000 nm, and it is merely a thiourea derivative, a thioamide derivative, a copper compound, a tungsten hexachloride and a trichloride. Since the same is true even when the alkyl or triaryl phosphate is simply mixed, a mixture containing a thiourea derivative or a thioamide derivative, a copper compound, and tungsten hexachloride and a trialkyl or triaryl phosphate is mixed by the above mixing method. By heating and kneading, thiourea derivative or thioamide derivative It is presumed that some kind of reaction occurred between the compound, the copper compound, tungsten hexachloride and the trialkyl or triaryl phosphate to form a complex.
【0021】[0021]
【実施例】以下に実施例を掲げて、本発明の詳細を述べ
るが、本発明はこれらの実施例に制限されるものではな
い。尚、実施例中の添加割合は全て重量部を示す。ま
た、得られた樹脂材料の透過スペクトルは、分光光度計
((株)日立製作所製:323 型) で測定した。近赤外線
吸収能の判定は、900 、1000、1100、及び1500nmの各波
長での吸収値の平均が80%以上のものを◎、60%以上を
○、30%以上を△、30%以下を×とし、行った。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, all the addition rates in an Example show a weight part. The transmission spectrum of the obtained resin material was measured with a spectrophotometer (type 323, manufactured by Hitachi, Ltd.). Judgment of near-infrared absorptivity was made when the average of the absorption values at each wavelength of 900, 1000, 1100, and 1500 nm was 80% or more: ◎, 60% or more: ○, 30% or more: Δ, 30% or less X, and performed.
【0022】近赤外線吸収能の熱、湿度、光に対する安
定性を下記の方法で測定した。 耐熱性・耐湿性:近赤外線吸収性シートを80℃、 100%
RHのオーブン中に 480時間放置した後、近赤外線吸収性
を再度分光光度計 (波長:1000nm) で測定した。そのシ
ートの保存性は、下記式により算出した結果で評価し
た。The stability of the near-infrared absorptivity to heat, humidity and light was measured by the following method. Heat / moisture resistance: Near infrared absorbing sheet at 80 ℃, 100%
After standing in a RH oven for 480 hours, near-infrared absorption was measured again with a spectrophotometer (wavelength: 1000 nm). The storability of the sheet was evaluated based on the result calculated by the following equation.
【0023】[0023]
【数1】 (Equation 1)
【0024】耐光性:近赤外線吸収性シートをUV(紫
外線)テスター(大日本プラスチック(株)製、超促進
耐光試験機)で 200時間光照射した後、近赤外線吸収性
を再度分光光度計 (波長:1000nm) で測定した。その保
存性は、下記式により算出した結果で評価した。Lightfastness: After irradiating the near-infrared absorbing sheet with a UV (ultraviolet) tester (super-accelerated lightfastness tester manufactured by Dainippon Plastics Co., Ltd.) for 200 hours, the near-infrared absorbing property was measured again by a spectrophotometer ( (Wavelength: 1000 nm). The storage stability was evaluated based on the result calculated by the following equation.
【0025】[0025]
【数2】 (Equation 2)
【0026】熱安定性は、射出成形機を用いて 230℃の
設定温度で滞留時間20分後成形を実施し、得られたサン
プルの色調変化を日本電色(株)製色差計にて測定し、
L.a.b.法により色差(△E)を求め、以下のように判定し
た。 ◎:優良 ○:良好 △:ヤケ無(黄色変化大) ×:ヤケ有実施例1〜24 表1、表2に示す組み合わせのチオ尿素化合物2重量部
と銅化合物0.2 重量部及び六塩化タングステン 0.1重量
部とトリアルキル又はトリアリールフォスフェート 0.5
重量部のそれぞれとスチレン樹脂100 重量部を、タンブ
ラーミキサーで20分間混合し、40mmφ押出成型機によっ
て 220℃で混練後、ペレットにした。次いでこのペレッ
トを乾燥し、射出成型機を用いて厚さ3mmのヘイズのな
い緑色の透明樹脂シートを作製した。得られたこれらの
シートについて 800〜2000nmにおける透過スペクトルを
測定した。表4に結果を示すが、近赤外域の吸収能に優
れていた。実施例1で得られた得られた近赤外線吸収性
シートの遮熱効果を図1に示した装置を用いて測定し
た。1は60Wの白熱電球、2は測定試料、3は精密温度
計である。その結果は図2の通りであった。近赤外線吸
収性シートの遮熱効果を図中のAで示すが、同図に示す
近赤外線吸収剤を含まない通常のポリスチレン樹脂の遮
熱効果を示したBとの比較から、近赤外域の遮熱能に優
れていることが分かる。また、実施例1で得られた透明
樹脂シートの透過スペクトルを図3中のAで示すが、同
図に示す近赤外線吸収剤を含まない通常のポリスチレン
樹脂シートの透過スペクトルBとの比較から分かるよう
に、この樹脂板は可視域の光は比較的よく透過するが、
通常のポリスチレン樹脂シートに見られない近赤外域の
吸収能に優れていた。The thermal stability was measured after a residence time of 20 minutes at a set temperature of 230 ° C. using an injection molding machine, and the color tone change of the obtained sample was measured with a color difference meter manufactured by Nippon Denshoku Co., Ltd. And
The color difference (ΔE) was determined by the Lab method and determined as follows. :: excellent :: good △: no burn (large yellow change) ×: burns Examples 1 to 24 2 parts by weight of thiourea compound, 0.2 parts by weight of copper compound and 0.1 parts by weight of tungsten hexachloride in the combinations shown in Tables 1 and 2 Parts by weight and trialkyl or triaryl phosphate 0.5
The respective parts by weight and 100 parts by weight of the styrene resin were mixed for 20 minutes by a tumbler mixer, kneaded at 220 ° C. by a 40 mmφ extruder, and formed into pellets. Next, the pellets were dried, and a 3 mm-thick green transparent resin sheet having no haze was prepared using an injection molding machine. The transmission spectra at 800 to 2000 nm of the obtained sheets were measured. The results are shown in Table 4, and the absorption ability in the near infrared region was excellent. The heat shielding effect of the near-infrared absorbing sheet obtained in Example 1 was measured using the apparatus shown in FIG. 1 is a 60 W incandescent lamp, 2 is a measurement sample, and 3 is a precision thermometer. The result was as shown in FIG. The heat-shielding effect of the near-infrared absorbing sheet is indicated by A in the figure. From the comparison with B, which shows the heat-shielding effect of a normal polystyrene resin containing no near-infrared absorbing agent shown in FIG. It turns out that it is excellent in heat-shielding ability. Further, the transmission spectrum of the transparent resin sheet obtained in Example 1 is shown by A in FIG. 3 and can be seen from a comparison with the transmission spectrum B of a normal polystyrene resin sheet containing no near-infrared absorber shown in FIG. As shown, this resin plate transmits light in the visible range relatively well,
It had excellent near-infrared absorption capacity not found in ordinary polystyrene resin sheets.
【0027】実施例25〜29 表2に示す組合わせのチオアミド化合物2重量部と銅化
合物 0.2重量部及び六塩化タングステン 0.1重量部とト
リアルキル又はトリアリールフォスフェート 0.5重量部
のそれぞれとポリスチレン樹脂 100重量部を、タンブラ
ーミキサーで20分間混合し、40mmφ押出成型機によって
220℃で混練後、ペレットにした。次いでこのペレット
を乾燥し、射出成型機を用いて厚さ3mmのヘイズのない
緑色の透明樹脂シートを作製した。得られたこれらのシ
ートについて 800〜2000nmにおける透過スペクトルを測
定した。表4、表5に結果を示すが、近赤外域の吸収能
に優れていた。 Examples 25 to 29 2 parts by weight of the thioamide compound, 0.2 parts by weight of the copper compound, 0.1 parts by weight of tungsten hexachloride, 0.5 parts by weight of trialkyl or triaryl phosphate and 100 parts by weight of the polystyrene resin in the combination shown in Table 2 Parts by weight, mix with a tumbler mixer for 20 minutes, and use a 40mmφ extruder
After kneading at 220 ° C., the mixture was formed into pellets. Next, the pellets were dried, and a 3 mm-thick green transparent resin sheet having no haze was prepared using an injection molding machine. The transmission spectra at 800 to 2000 nm of the obtained sheets were measured. Tables 4 and 5 show the results. The results were excellent in the near infrared absorption capacity.
【0028】[0028]
【表1】 [Table 1]
【0029】実施例30〜35 表2に示す組合わせのチオ尿素化合物2重量部と銅化合
物 0.2重量部及び六塩化タングステン 0.1重量部とトリ
アルキル又はトリアリールフォスフェート1重量部を下
記の処方で、 成 分 割合、重量部 (A) 液 チオ尿素化合物 2 銅化合物 0.2 10%ポリビニルアルコール水溶液 10 (B) 液 六塩化タングステン 0.1 トリアルキル又はトリアリールフォスフェート 0.5 エチルアルコール 10 (A) 液50重量部と(B) 液50重量部を混合し、ポリスチ
レン樹脂シートにワイヤーバーを用いて塗布量が5g/
m2になるように塗布乾燥させた。得られたポリスチレン
樹脂シートは、いずれも淡青色であり、塗工面を表面温
度 160℃にメタルブロックに5秒間接触させたところ、
淡緑色に発色した。得られたこれらの板について 800〜
2000nmにおける透過スペクトルを測定した。表5に結果
を示すが、近赤外域の吸収能に優れていた。 Examples 30-35 2 parts by weight of a thiourea compound, 0.2 parts by weight of a copper compound, 0.1 parts by weight of tungsten hexachloride and 1 part by weight of a trialkyl or triaryl phosphate in the combination shown in Table 2 were formulated according to the following formulation. , Component ratio, parts by weight (A) solution Thiourea compound 2 copper compound 0.2 10% aqueous polyvinyl alcohol solution 10 (B) solution tungsten hexachloride 0.1 trialkyl or triaryl phosphate 0.5 ethyl alcohol 10 (A) solution 50 parts by weight And 50 parts by weight of the liquid (B) were mixed, and a coating amount of 5 g /
It was applied and dried to obtain m 2 . Each of the obtained polystyrene resin sheets was light blue, and when the coated surface was brought into contact with the metal block at a surface temperature of 160 ° C. for 5 seconds,
It developed a pale green color. About these obtained boards 800-
The transmission spectrum at 2000 nm was measured. The results are shown in Table 5, and the absorption ability in the near infrared region was excellent.
【0030】実施例36〜41 表2に示す組合わせと重量部でチオ尿素化合物、銅化合
物、六塩化タングステンとトリアルキル又はトリアリー
ルフォスフェートをスチレン系樹脂 100重量部に添加
し、タンブラーミキサーで20分間混合し、40mmφ押出成
形機によって 220℃で混練後、ペレットにした。次いで
このペレットを乾燥し、射出成形機を用いて厚さ3mmの
ヘイズのない緑色の透明樹脂板を作製した。得られたこ
れらの板について 800〜2000nmにおける透過スペクトル
を測定した。表5に結果を示すが、近赤外域の吸収能に
優れていた。 Examples 36 to 41 The thiourea compound, copper compound, tungsten hexachloride and trialkyl or triaryl phosphate were added to 100 parts by weight of the styrene resin in the combinations and parts by weight shown in Table 2, and the mixture was mixed with a tumbler mixer. The mixture was mixed for 20 minutes, kneaded at 220 ° C by a 40 mmφ extruder, and formed into pellets. Then, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra at 800 to 2000 nm of the obtained plates were measured. The results are shown in Table 5, and the absorption ability in the near infrared region was excellent.
【0031】[0031]
【表2】 [Table 2]
【0032】比較例1〜10 表3に示すチオ尿素化合物、チオアミド化合物、銅化合
物、六塩化タングステン、トリアルキル又はトリアリー
ルフォスフェートを各々単独でポリスチレン樹脂 100重
量部に添加し、タンブラーミキサーで20分間混合し、40
mmφ押出成型機によって 220℃で混練後、ペレットにし
た。次いでこのペレットを乾燥し、射出成型機を用いて
厚さ3mmのヘイズのない緑色の透明樹脂板を作製した。
得られたこれらの板について透過スペクトルを測定し
た。表5に結果を示すが、全て30%以下の近赤外線吸収
能しかなかった。 Comparative Examples 1 to 10 Each of a thiourea compound, a thioamide compound, a copper compound, a tungsten hexachloride, a trialkyl or a triaryl phosphate shown in Table 3 was independently added to 100 parts by weight of a polystyrene resin. Mix for 40 minutes,
The mixture was kneaded at 220 ° C. by a mmφ extruder and then formed into pellets. Next, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine.
The transmission spectra of these obtained plates were measured. Table 5 shows the results, all of which had a near infrared absorption capacity of 30% or less.
【0033】比較例11〜12 表3に示す銅化合物 0.2重量部とトリアルキル又はトリ
アリールフォスフェート 0.5重量部をポリスチレン樹脂
100重量部に添加し、タンブラーミキサーで20分間混合
し、40mmφ押出成型機によって 220℃で混練後、ペレッ
トにした。次いでこのペレットを乾燥し、射出成型機を
用いて厚さ3mmのヘイズのない緑色の透明樹脂板を作製
した。得られたこれらの板について 800〜2000nmにおけ
る透過スペクトルを測定した。表5に結果を示すが、全
て30%以下の近赤外線吸収能しかなかった。 Comparative Examples 11 and 12 0.2 parts by weight of a copper compound shown in Table 3 and 0.5 parts by weight of a trialkyl or triaryl phosphate were mixed with a polystyrene resin.
The mixture was added to 100 parts by weight, mixed with a tumbler mixer for 20 minutes, kneaded at 220 ° C. with a 40 mmφ extrusion molding machine, and formed into pellets. Next, the pellets were dried, and a 3 mm-thick, haze-free green transparent resin plate was prepared using an injection molding machine. The transmission spectra at 800 to 2000 nm of the obtained plates were measured. Table 5 shows the results, all of which had a near infrared absorption capacity of 30% or less.
【0034】[0034]
【表3】 [Table 3]
【0035】[0035]
【表4】 [Table 4]
【0036】[0036]
【表5】 [Table 5]
【0037】表4、表5によれば、チオ尿素化合物又は
チオアミド化合物と銅化合物及び六塩化タングステンと
トリアルキル又はトリアリールフォスフェートとを塗布
或は加熱混練された成形体は、強い近赤外線吸収能を有
することが明らかである。また、この近赤外線吸収性
は、加熱や加湿或は露光によって殆ど低下せず、取扱い
や保存の環境条件の変化に対して安定性が高いものであ
ることが分かる。尚、チオ尿素化合物、チオアミド化合
物、銅化合物、六塩化タングステン或はトリアルキル又
はトリアリールフォスフェートとを単独に混練した成形
体は、近赤外線吸収性を実質的に示さなかった。According to Tables 4 and 5, a molded product obtained by coating or heating and kneading a thiourea compound or a thioamide compound with a copper compound and tungsten hexachloride with a trialkyl or triaryl phosphate has a strong near-infrared absorption. It is clear that it has a function. The near-infrared absorptivity hardly decreases due to heating, humidification, or exposure, and it is understood that the near-infrared absorption is highly stable against changes in environmental conditions of handling and storage. In addition, a molded article obtained by kneading a thiourea compound, a thioamide compound, a copper compound, tungsten hexachloride or a trialkyl or triaryl phosphate alone did not substantially exhibit near-infrared absorption.
【0038】[0038]
【発明の効果】本発明の近赤外線吸収剤用樹脂組成物を
加熱処理して得られる吸収材料及びその成形体は褪色な
どの不安定性はなく、暗所に長期間放置により褪色する
というフォトクロミズムも見られず、優れた近赤外線吸
収能を示すので、光学的フィルター、熱線吸収性グレー
ジング材等として工業的に有用である。また、得られた
近赤外線吸収シートは 800〜2000nmの近赤外領域全域に
渡る強い吸収性を有している。これらの性質を利用する
ことによって近赤外線カットフィルターなどの光学材
料、記録材料、熱線遮蔽材料、蓄熱材料、近赤外線検出
センサー等として利用できる。本発明の組成物は、金属
を含んでいるにもかかわらず、着色が少ないから、これ
らを含有したシート、フィルム等の成形体は外観が優れ
たものとなる。According to the present invention, the absorbing material obtained by heat-treating the resin composition for near-infrared absorbing agent of the present invention and the molded product thereof have no instability such as discoloration, and have a photochromism that discolors when left in a dark place for a long time. Since it is not seen and exhibits excellent near-infrared absorbing ability, it is industrially useful as an optical filter, a heat ray absorbing glazing material and the like. Moreover, the obtained near-infrared absorbing sheet has strong absorptivity over the entire near-infrared region of 800 to 2000 nm. By utilizing these properties, it can be used as an optical material such as a near infrared cut filter, a recording material, a heat ray shielding material, a heat storage material, a near infrared detection sensor, and the like. Since the composition of the present invention contains a metal but has little coloring, molded articles such as sheets and films containing these have excellent appearance.
【図1】近赤外線吸収性シートの遮熱効果を測定する装
置の概略図である。FIG. 1 is a schematic view of an apparatus for measuring a heat shielding effect of a near-infrared absorbing sheet.
【図2】遮熱効果の測定結果を示す図である。FIG. 2 is a diagram showing measurement results of a heat shielding effect.
【図3】透過スペクトルを示す図であるFIG. 3 is a diagram showing a transmission spectrum.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C08K 5/41 C08K 5/41 5/53 5/53 G02B 5/22 G02B 5/22 G11B 7/24 526 G11B 7/24 526P (58)調査した分野(Int.Cl.7,DB名) C09K 3/00 105 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI C08K 5/41 C08K 5/41 5/53 5/53 G02B 5/22 G02B 5/22 G11B 7/24 526 G11B 7/24 526P (58) Field surveyed (Int. Cl. 7 , DB name) C09K 3/00 105
Claims (6)
リール基、アラルキル基及び複素環残基(各基は1個以
上の置換基を有していても良い)から成る群から選ばれ
る一価基,X は−COO,−SO4,−SO3,−PO4,−O 、n は1
〜4の整数〕で表わされる銅化合物、或はクロロフィル
銅、銅クロロフィリンナトリウム及びビスアセチルアセ
トナート銅より成る群から選ばれる少なくとも一種の銅
化合物1重量部に対して下記一般式(II) 【化1】 (R1, R2,R3は、水素、アルキル基、シクロアルキル
基、アリール基、アラルキル基及び5員又は6員の複素
環残基から成る群から選ばれる一価基を表わし、各基は
1個以上の置換基を有していても良く、R1とR2又はR2と
R3は連結して環を形成しても良い) で示されるチオ尿素
誘導体から選ばれる少なくとも一種0.05〜50重量部から
成る成分又は下記一般式(III) 【化2】 (R 4 ,R 5 は、水素、アルキル基、アルケニル基、シクロ
アルキル基、アリール基、アラルキル基及び5員又は6
員の複素環残基から成る群から選ばれる一価基を表わ
し、R 5 は更にアルコキシ基をも表わし、各基は1個以上
の置換基を有していても良く、R 4 とR 5 は連結して環を形
成しても良い) で示されるチオアミド誘導体から選ばれ
る少なくとも1種のチオアミド誘導体0.05〜50重量部か
ら成る成分20 〜80重量%と、 (B) 六塩化タングステン1重量部に対してトリアルキル
又はトリアリールフォスフェート0.05〜10重量部から成
る成分80〜20重量%から成り、(A) +(B) = 100重量%
である近赤外線吸収剤用組成物。(A) A compound represented by the general formula (I) (R-X) n Cu (I) wherein R is hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and a heterocyclic residue (each monovalent radical groups selected from the group consisting of which may have one or more substituents), X is -COO, -SO 4, -SO 3, -PO 4, -O, n is 1
To an integer of 4 to 1 part by weight of at least one copper compound selected from the group consisting of copper chlorophyll, copper copper chlorophyllin and copper bisacetylacetonate. 1) (R 1 , R 2 , and R 3 each represent a monovalent group selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a 5- or 6-membered heterocyclic residue. May have one or more substituents, and R 1 and R 2 or R 2
R 3 may be linked to form a ring) at least one component selected from the group consisting of 0.05 to 50 parts by weight selected from the group consisting of thiourea derivatives represented by the following general formulas (III) : (R 4 and R 5 represent hydrogen, an alkyl group, an alkenyl group,
Alkyl group, aryl group, aralkyl group and 5 or 6 members
Represents a monovalent group selected from the group consisting of
And R 5 also represents an alkoxy group, and each group is at least one
R 4 and R 5 may be linked to form a ring
Or a thioamide derivative represented by
0.05 to 50 parts by weight of at least one thioamide derivative
(A) + (A) + (B) 20 to 80% by weight of a component consisting of (B) 0.05 to 10 parts by weight of a trialkyl or triaryl phosphate per 1 part by weight of tungsten hexachloride; B) = 100% by weight
A composition for a near infrared absorber.
を含有させたことを特徴とする近赤外線吸収材料。2. A near-infrared absorbing material, comprising the composition for a near-infrared absorbing agent according to claim 1 .
を加熱処理して得られる反応物から成る近赤外線吸収材
料。3. A near-infrared absorbing material comprising a reaction product obtained by heat-treating the composition for a near-infrared absorbing agent according to claim 1 .
を加熱しながら含有させたことを特徴とする近赤外線吸
収成形体。4. A near-infrared absorbing molded article comprising the composition for a near-infrared absorbing agent according to claim 1 while heating.
させたことを特徴とする近赤外線吸収用成形体。5. A molded article for absorbing near-infrared rays, comprising the near-infrared ray absorbing material according to claim 3 .
して成る近赤外線吸収成形体。6. A near-infrared absorbing molded product obtained by heating the near-infrared absorbing material according to claim 2 .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00032792A JP3150745B2 (en) | 1992-01-06 | 1992-01-06 | Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing them |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP00032792A JP3150745B2 (en) | 1992-01-06 | 1992-01-06 | Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing them |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05179228A JPH05179228A (en) | 1993-07-20 |
JP3150745B2 true JP3150745B2 (en) | 2001-03-26 |
Family
ID=11470814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP00032792A Expired - Fee Related JP3150745B2 (en) | 1992-01-06 | 1992-01-06 | Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing them |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3150745B2 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6229252B1 (en) * | 1999-01-21 | 2001-05-08 | Asahi Glass Company, Limited | Dye combinations for multiple bandpass filters for video displays |
JP3809835B2 (en) * | 2003-12-26 | 2006-08-16 | 東洋紡績株式会社 | Manufacturing method of near-infrared absorbing film |
JP3809836B2 (en) * | 2003-12-26 | 2006-08-16 | 東洋紡績株式会社 | Manufacturing method of near-infrared absorbing film |
JP4689987B2 (en) * | 2003-08-29 | 2011-06-01 | 三菱樹脂株式会社 | Transparent resin composition that absorbs near infrared rays |
JP3852444B2 (en) * | 2003-12-26 | 2006-11-29 | 東洋紡績株式会社 | Method for producing wavelength selective absorption film |
JP2006184892A (en) * | 2005-11-30 | 2006-07-13 | Toyobo Co Ltd | Near-infrared absorption film |
JP2008018585A (en) * | 2006-07-12 | 2008-01-31 | Mitsubishi Plastics Ind Ltd | Manufacturing method of resin molded body having near infrared absorbability |
CN104169750B (en) * | 2012-03-16 | 2017-07-25 | 富士胶片株式会社 | Infrared shield film |
JP5878059B2 (en) * | 2012-03-29 | 2016-03-08 | 富士フイルム株式会社 | Infrared shielding film |
JP5878050B2 (en) * | 2012-03-16 | 2016-03-08 | 富士フイルム株式会社 | Heat ray shielding material |
JP2014214296A (en) * | 2013-04-30 | 2014-11-17 | 旭硝子株式会社 | Near-infrared ray absorbing particle, dispersion liquid, and article of the particle |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2505859B2 (en) * | 1988-06-13 | 1996-06-12 | 日本製紙株式会社 | Composition for near-infrared absorbing agent, as well as near-infrared absorbing material and molded article containing them |
JPH0781127B2 (en) * | 1988-07-22 | 1995-08-30 | 日本製紙株式会社 | Composition for near-infrared absorbing agent, as well as near-infrared absorbing material and molded article containing them |
JP2882641B2 (en) * | 1989-06-30 | 1999-04-12 | 株式会社クラレ | Near-infrared absorbing modifier and method for producing the same |
-
1992
- 1992-01-06 JP JP00032792A patent/JP3150745B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH05179228A (en) | 1993-07-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3150745B2 (en) | Composition for near-infrared absorbing agent, near-infrared absorbing material, and molded article containing them | |
JP3206940B2 (en) | Near-infrared absorbing methacrylic resin composition and molded article thereof | |
US3382183A (en) | Plastic optical filter | |
US2307092A (en) | Stabilized artificial resins | |
EP0467552B1 (en) | Photochromic compositions | |
US3341464A (en) | Heat resistant aminium salt infrared absorbers | |
JPH0234682A (en) | Composition for near-infrared absorber, near-infrared absorber and molded product containing same | |
JP3224869B2 (en) | Near-infrared absorbing transparent resin composition and molded article thereof | |
US3049509A (en) | Heterocyclic ultraviolet absorbers | |
DE69409688T2 (en) | Dimerized thiourea derivatives, near infrared absorbing agents containing them, and heat radiation shielding materials containing them | |
CA1055504A (en) | Polychromophoric heterocyclic ultraviolet stabilizers and their use in organic compositions | |
JPH05239452A (en) | Stabilizing mixture for compound having photochromic activity | |
JP3088161B2 (en) | Near-infrared absorbing styrene resin composition and molded article thereof | |
US3600397A (en) | Certain benzotriazolylphenoxy tin compounds | |
JPH05163426A (en) | Near infrared ray-absorbing polycarbonate resin composition and its form | |
JPH05163405A (en) | Near-infrared absorbing vinyl chloride-based resin composition and its molding | |
JP2505859B2 (en) | Composition for near-infrared absorbing agent, as well as near-infrared absorbing material and molded article containing them | |
US2874146A (en) | Polymeric compositions | |
US3389004A (en) | Ultraviolet light stabilizers for plastic materials | |
JP2790629B2 (en) | Photochromic transparent molded body | |
US3557012A (en) | Heat-stabilized infrared absorbers and compositions containing the same | |
JP2003096040A (en) | Diimonium salt compound and near-infrared ray absorption filter using the same | |
JP2724032B2 (en) | Photochromic composition | |
CA1334624C (en) | Near infrared absorbing composition and material and product containing same | |
JP6855363B2 (en) | Optical filters and compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080119 Year of fee payment: 7 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080119 Year of fee payment: 7 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090119 Year of fee payment: 8 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100119 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100119 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110119 Year of fee payment: 10 |
|
LAPS | Cancellation because of no payment of annual fees |