JP7335975B2 - 感光性インク組成物、硬化物、ディスプレイパネル、及び硬化物の製造方法 - Google Patents
感光性インク組成物、硬化物、ディスプレイパネル、及び硬化物の製造方法 Download PDFInfo
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- JP7335975B2 JP7335975B2 JP2021561388A JP2021561388A JP7335975B2 JP 7335975 B2 JP7335975 B2 JP 7335975B2 JP 2021561388 A JP2021561388 A JP 2021561388A JP 2021561388 A JP2021561388 A JP 2021561388A JP 7335975 B2 JP7335975 B2 JP 7335975B2
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- 239000000203 mixture Substances 0.000 title claims description 127
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- -1 sulfide compound Chemical class 0.000 claims description 581
- 125000004432 carbon atom Chemical group C* 0.000 claims description 214
- 125000000217 alkyl group Chemical group 0.000 claims description 144
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 127
- 125000000962 organic group Chemical group 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 56
- 125000003545 alkoxy group Chemical group 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 239000003999 initiator Substances 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 24
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 239000011817 metal compound particle Substances 0.000 claims description 13
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- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 8
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 6
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000862 absorption spectrum Methods 0.000 claims description 3
- 230000008033 biological extinction Effects 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005083 Zinc sulfide Substances 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 description 199
- 125000000623 heterocyclic group Chemical group 0.000 description 71
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- 125000003118 aryl group Chemical group 0.000 description 22
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- 229910052736 halogen Inorganic materials 0.000 description 14
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
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- 125000006517 heterocyclyl carbonyl group Chemical group 0.000 description 9
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- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 8
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 8
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 8
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 8
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 8
- 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 8
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 7
- 125000004663 dialkyl amino group Chemical group 0.000 description 7
- 229910052731 fluorine Inorganic materials 0.000 description 7
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
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- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000001316 cycloalkyl alkyl group Chemical group 0.000 description 5
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
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- 229940059574 pentaerithrityl Drugs 0.000 description 5
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 4
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- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
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- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 4
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 4
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
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- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 4
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 4
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 4
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000001352 cyclobutyloxy group Chemical group C1(CCC1)O* 0.000 description 3
- 125000003113 cycloheptyloxy group Chemical group C1(CCCCCC1)O* 0.000 description 3
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- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
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- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
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Classifications
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- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
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- G03F7/2018—Masking pattern obtained by selective application of an ink or a toner, e.g. ink jet printing
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
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- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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Description
このような高屈折材料として、加水分解性シリル基を有する特定の構造のフルオレン化合物で処理された金属酸化物粒子と、アクリロイル基を有する特定の構造のフルオレン化合物と、光重合開始剤と、有機溶媒とを含む組成物が、開示されている(特許文献1の実施例を参照)。
光重合性化合物(A)が、下記式(a-1)で表されるスルフィド化合物(A1)と、下記式(a-2)で表される(メタ)アクリレート化合物(A2)とを含み、
光重合開始剤(C)が、フォスフィンオキサイド化合物(C1)と、オキシムエステル化合物(C2)とを組み合わせて含む、感光性インク組成物である。
成形された感光性インク組成物に対して露光することと、
を含む硬化物の製造方法である。
感光性インク組成物は、光重合性化合物(A)と、光重合開始剤(C)とを含む。感光性インク組成物は、溶媒(S)を含むか、又は含まない。
光重合性化合物(A)は、後述する式(a-1)で表されるスルフィド化合物(A1)と、後述する式(a-2)で表される(メタ)アクリレート化合物(A2)とを含む。
光重開始剤(C)は、フォスフィンオキサイド化合物(C1)と、オキシムエステル化合物(C2)とを組み合わせて含む。
感光性インク組成物は、光重合性化合物(A)を含む。光重合性化合物(A)は、後述する式(a-1)で表されるスルフィド化合物(A1)と、後述する式(a-2)で表される(メタ)アクリレート化合物(A2)とを含む。
スルフィド化合物(A1)は、下記式(a-1)で表される化合物である。
(メタ)アクリレート化合物(A2)は、下記式(a-2)で表される化合物である。
アルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロピルオキシ基、イソプロピルオキシ基、n-ブチルオキシ基、イソブチルオキシ基、sec-ブチルオキシ基、及びtert-ブチルオキシ基が挙げられる。これらの中では、メトキシ基、及びエトキシ基が好ましく、メトキシ基がより好ましい。
sは、0以上5以下の整数であり、0又は1が好ましく、0がより好ましい。
光重合性化合物(A)は、本発明の目的を阻害しない範囲で、スルフィド化合物(A1)、及び(メタ)アクリレート化合物(A2)以外のその他の光重合性化合物(A3)を含んでいてもよい。
その他の光重合性化合物(A3)としては、特に限定されず、従来公知の単官能光重合性化合物、及び多官能光重合性化合物を用いることができる。
感光性インク組成物の溶媒(S)の質量を除いた質量に対する、スルフィド化合物(A1)の質量の比率は、5質量%以上30質量%以下が好ましく、7質量%以上25質量%以下がより好ましく、9質量%以上20質量%以下がさらに好ましい。
感光性インク組成物の溶媒(S)の質量を除いた質量に対する、(メタ)アクリレート化合物(A2)の質量の比率は、10質量%以上50質量%以下が好ましく、20質量%以上45質量%以下がより好ましく、30質量%以上40質量%以下がさらに好ましい。
光重合性化合物(A)が、上記の範囲内の量のスルフィド化合物(A1)及び(メタ)アクリレート化合物(A2)を含むことにより、感光性インク組成物が光硬化性に優れ、且つ低粘度であり、感光性インク組成物を用いて高い屈折率の硬化物を形成できる。
また、スルフィド化合物(A1)の質量MA1と(メタ)アクリレート化合物(A2)の質量MA2との比(MA1:MA2)は、光硬化性、粘度、及び硬化物の屈折率のバランスの点で、1:99~59:41が好ましく、5:95~55:45がより好ましく、10:90~53:47がさらに好ましく、15:85~50:50が特に好ましい。
感光性インク組成物は、金属化合物粒子(B)を含むのが好ましい。金属化合物粒子(B)は、酸化チタン粒子、チタン酸バリウム粒子、酸化セリウム粒子、及び硫化亜鉛粒子からなる群より選択される少なくとも1種である。感光性インク組成物は、これらの金属化合物粒子(B)のうちの1種を単独で含んでもよく、2種以上を組み合わせて含んでいてもよい。
感光性インク組成物が、上記の金属化合物粒子(B)を含む場合、高屈折率を示す硬化物の形成が特に容易である。
感光性インク組成物中の金属化合物粒子(B)の含有量が上記の範囲内であることにより、感光性インク組成物が溶媒(S)を含んでいない場合でも低粘度の感光性インク組成物を得やすく、また、高屈折率の硬化物を形成しやすい。
感光性インク組成物は、光重合開始剤(C)として、フォスフィンオキサイド化合物(C1)と、オキシムエステル化合物(C2)とを組み合わせて含む。
かかる光重合開始剤(C)を用いることにより、感光性インク組成物を用いて、高い屈折率と高い透明性とを兼ね備える硬化物を形成できる。フォスフィンオキサイド化合物(C1)と、オキシムエステル化合物(C2)とを組み合わせて含む光重合開始剤(C)は、特に硬化物の透明性に寄与する。
所望する効果を得やすい点から、光重合開始剤(C)の質量に対する、フォスフィンオキサイド化合物(C1)の質量と、オキシムエステル化合物(C2)の質量との合計の比率は、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましく、100質量%が特に好ましい。
フォスフィンオキサイド化合物(C1)は、P=O結合を有する5価リン化合物である。フォスフィンオキサイド化合物(C1)として、従来より光重合開始剤として使用されているP=O結合を有する5価リン化合物を特に制限なく用いることができる。
フォスフィンオキサイド化合物の例としては、下記式(c-I)で表される部分構造を有する化合物が挙げられる。
アルキル基の具体例としては、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、sec-ブチル基、tert-ブチル基、n-ペンチル基、イソペンチル基、tert-ペンチル基、n-ヘキシル基、n-ヘプチル基、n-オクチル基、2,4,4,-トリメチルペンチル基、2-エチルヘキシル基、n-ノニル基、n-デシル基、n-ウンデシル基、及びn-ドデシル基が挙げられる。
脂肪族アシル基の具体例としては、アセチル基、プロピオニル基、ブタノイル基、ペンタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ウンデカノイル基、ドデカノイル基、トリデカノイル基、テトラデカノイル基、ペンタデカノイル基、ヘキサデカノイル基、ヘプタデカノイル基、オクタデカノイル基、ノナデカノイル基、及びイコサノイル基が挙げられる。
オキシムエステル化合物(C2)は、>C=N-O-CO-で表される結合を有する化合物である。オキシムエステル化合物(C2)として、従来より光重合開始剤として使用されている、>C=N-O-CO-で表される結合を有する化合物を特に制限なく用いることができる。
アルキル基が炭素原子上に有してもよい好適な置換基の例としては、炭素原子数1以上20以下のアルコキシ基、炭素原子数3以上10以下のシクロアルキル基、炭素原子数3以上10以下のシクロアルコキシ基、炭素原子数2以上20以下の飽和脂肪族アシル基、炭素原子数2以上20以下のアルコキシカルボニル基、炭素原子数2以上20以下の飽和脂肪族アシルオキシ基、置換基を有してもよいフェニル基、置換基を有してもよいフェノキシ基、置換基を有してもよいフェニルチオ基、置換基を有してもよいベンゾイル基、置換基を有してもよいフェノキシカルボニル基、置換基を有してもよいベンゾイルオキシ基、置換基を有してもよい炭素原子数7以上20以下のフェニルアルキル基、置換基を有してもよいナフチル基、置換基を有してもよいナフトキシ基、置換基を有してもよいナフトイル基、置換基を有してもよいナフトキシカルボニル基、置換基を有してもよいナフトイルオキシ基、置換基を有してもよい炭素原子数11以上20以下のナフチルアルキル基、置換基を有してもよいヘテロシクリル基、置換基を有してもよいヘテロシクリルカルボニル基、アミノ基、1又は2の有機基で置換されたアミノ基、モルホリン-1-イル基、及びピペラジン-1-イル基、ハロゲン、ニトロ基、及びシアノ基等が挙げられる。
フェニル基が炭素原子上に有してもよい好適な置換基の例としては、アルキル基が炭素原子上に有してもよい好適な置換基として上記で例示した基に加えて、炭素原子数1以上20以下のアルキル基が挙げられる。
また、Rc1が水素原子であると、透明性が良好となる傾向があり好ましい。なお、Rc1が水素原子であり且つRc4が後述の式(1a)又は(1b)で表される基であると透明性はより良好となる傾向がある。
アルキル基が有してもよい置換基は、本発明の目的を阻害しない範囲で特に限定されない。置換基の好適な例としては、シアノ基、ハロゲン原子、環状有機基、及びアルコキシカルボニル基が挙げられる。ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。これらの中では、フッ素原子、塩素原子、臭素原子が好ましい。環状有機基としては、シクロアルキル基、芳香族炭化水素基、ヘテロシクリル基が挙げられる。シクロアルキル基の具体例としては、Rc1がシクロアルキル基である場合の好適な例と同様である。芳香族炭化水素基の具体例としては、フェニル基、ナフチル基、ビフェニリル基、アントリル基、及びフェナントリル基等が挙げられる。ヘテロシクリル基の具体例としては、Rc1がヘテロシクリル基である場合の好適な例と同様である。Rc1がアルコキシカルボニル基である場合、アルコキシカルボニル基に含まれるアルコキシ基は、直鎖状でも分岐鎖状でもよく、直鎖状が好ましい。アルコキシカルボニル基に含まれるアルコキシ基の炭素原子数は、1以上10以下が好ましく、1以上6以下がより好ましい。
その他の光重合開始剤(C3)として具体的には、1-ヒドロキシシクロヘキシルフェニルケトン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-〔4-(2-ヒドロキシエトキシ)フェニル〕-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、1-(4-イソプロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、1-(4-ドデシルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、ビス(4-ジメチルアミノフェニル)ケトン、2-メチル-1-〔4-(メチルチオ)フェニル〕-2-モルフォリノプロパン-1-オン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタン-1-オン、4-ベンゾイル-4’-メチルジメチルスルフィド、4-ジメチルアミノ安息香酸、4-ジメチルアミノ安息香酸メチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸ブチル、4-ジメチルアミノ-2-エチルヘキシル安息香酸、4-ジメチルアミノ-2-イソアミル安息香酸、ベンジル-β-メトキシエチルアセタール、ベンジルジメチルケタール、1-フェニル-1,2-プロパンジオン-2-(O-エトキシカルボニル)オキシム、o-ベンゾイル安息香酸メチル、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、1-クロロ-4-プロポキシチオキサントン、チオキサンテン、2-クロロチオキサンテン、2,4-ジエチルチオキサンテン、2-メチルチオキサンテン、2-イソプロピルチオキサンテン、2-エチルアントラキノン、オクタメチルアントラキノン、1,2-ベンズアントラキノン、2,3-ジフェニルアントラキノン、アゾビスイソブチロニトリル、ベンゾイルパーオキシド、クメンヒドロペルオキシド、2-メルカプトベンゾイミダゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾチアゾール、2-(o-クロロフェニル)-4,5-ジ(m-メトキシフェニル)-イミダゾリル二量体、ベンゾフェノン、2-クロロベンゾフェノン、p,p’-ビスジメチルアミノベンゾフェノン、4,4’-ビスジエチルアミノベンゾフェノン、4,4’-ジクロロベンゾフェノン、3,3-ジメチル-4-メトキシベンゾフェノン、ベンジル、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン-n-ブチルエーテル、ベンゾインイソブチルエーテル、ベンゾインブチルエーテル、アセトフェノン、2,2-ジエトキシアセトフェノン、p-ジメチルアセトフェノン、p-ジメチルアミノプロピオフェノン、ジクロロアセトフェノン、トリクロロアセトフェノン、p-tert-ブチルアセトフェノン、p-ジメチルアミノアセトフェノン、p-tert-ブチルトリクロロアセトフェノン、p-tert-ブチルジクロロアセトフェノン、α,α-ジクロロ-4-フェノキシアセトフェノン、チオキサントン、2-メチルチオキサントン、2-イソプロピルチオキサントン、ジベンゾスベロン、ペンチル-4-ジメチルアミノベンゾエート、9-フェニルアクリジン、1,7-ビス-(9-アクリジニル)ヘプタン、1,5-ビス-(9-アクリジニル)ペンタン、1,3-ビス-(9-アクリジニル)プロパン、p-メトキシトリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-[2-(5-メチルフラン-2-イル)エテニル]-4,6-ビス(トリクロロメチル)-s-トリアジン、2-[2-(フラン-2-イル)エテニル]-4,6-ビス(トリクロロメチル)-s-トリアジン、2-[2-(4-ジエチルアミノ-2-メチルフェニル)エテニル]-4,6-ビス(トリクロロメチル)-s-トリアジン、2-[2-(3,4-ジメトキシフェニル)エテニル]-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-エトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-n-ブトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4-ビス-トリクロロメチル-6-(3-ブロモ-4-メトキシ)フェニル-s-トリアジン、2,4-ビス-トリクロロメチル-6-(2-ブロモ-4-メトキシ)フェニル-s-トリアジン、2,4-ビス-トリクロロメチル-6-(3-ブロモ-4-メトキシ)スチリルフェニル-s-トリアジン、2,4-ビス-トリクロロメチル-6-(2-ブロモ-4-メトキシ)スチリルフェニル-s-トリアジン等が挙げられる。
感光性インク組成物は、感光性インク組成物の質量に対して5質量%以下の溶媒(S)を含んでいてもよい。溶媒(S)の種類は特に限定されないが、典型的には有機溶媒である。
この場合、ディスプレイパネルを構成する種々の部材にダメージを与えないために、高屈折率膜形成時の溶媒(S)の揮発や、高屈折率膜に残留する溶媒(S)に由来するアウトガスの発生が少ないことが望まれる。
溶媒(S)の揮発やアウトガスの問題は、感光性インク組成物における溶媒(S)の含有量を低減することにより解消され得る。しかし、一般的には、感光性組成物等において溶媒の含有量を低減する場合、組成物の塗布性が著しく損なわれ、特にインクジェット法等の塗布方法への適用が困難である。
感光性インク組成物の粘度は、例えば、光重合性化合物(A)、金属化合物粒子(B)及び溶媒(S)等の含有量を調整すること等によって調整することができる。
感光性インク組成物は、溶媒(S)を実質的に含まないのが最も好ましい。感光性インク組成物が溶媒(S)を実質的に含まないとは、原料等に付随してごく少量の溶媒(S)が不可避的に感光性インク組成物に持ち込まれる他、感光性インク組成物に意図的に溶媒(S)が加えられていないことを言う。
感光性インク組成物が溶媒(S)を実質的に含まない場合の、感光性組成物の溶媒(S)の含有量は、例えば0.2質量%以下であり、0.15質量%以下が好ましく、0.1質量%以下がより好ましく、0.05質量%以下がさらに好ましい。
感光性インク組成物は、本発明の目的を阻害しない範囲で、以上説明した成分の他に、従来から感光性組成物やインク組成物に配合されている種々の添加剤を含んでいてもよい。感光性インク祖組成物に配合される好ましい添加剤としては、分散剤、シランカップリング剤等の密着促進剤、酸化防止剤、凝集防止剤、消泡剤、界面活性剤等が挙げられる。界面活性剤としては、特に限定されず、フッ素系界面活性剤、シリコン系界面活性剤等の公知の成分を用いることができる。
以上説明した成分を、それぞれ所定量混合したのち、混合物を均一に撹拌することにより感光性インク組成物が得られる。
以上説明した感光性インク組成物は、典型的には、
感光性インク組成物を、形成される硬化物の形状に応じて成形することと、
成形された感光性インク組成物に対して露光することと、
を含む方法によって、硬化物とされる。
例えば、前述の感光性インク組成物の硬化物からなる膜は、有機ELディスプレイパネルや、液晶ディスプレイパネル等の種々のディスプレイパネルにおいて反射防止膜等を構成する高屈折率膜として好適に使用される。
感光性インク組成物を成形する方法としては、特に限定されない。硬化物の形状がレンズ形状やプリズム形状等である場合には、硬化物の形状に応じた鋳型中に感光性インク組成物をスキージ等を用いて充填してもよい。
硬化物の形状がライン形状等である場合、硬化物の形状に応じて、基材上に感光性インク組成物を塗布すればよい。塗布方法としては、例えば、インクジェット法等の印刷法が挙げられる。
硬化物を膜形状に塗布する方法としては、ロールコータ、リバースコータ、バーコータ等の接触転写型塗布装置や、スピンナー(回転式塗布装置)、カーテンフローコータ等の非接触型塗布装置を用いる方法が挙げられる。また、インクジェット法等の印刷法によって感光性インク組成物を膜形状に塗布することもできる。
また、前述の感光性インク組成物を、3Dプリンティング法に適用して、インクジェット印刷と、露光による硬化とを繰り返して薄膜状の硬化物を積層することにより、所望する形状の硬化物を形成してもよい。
成形された感光性インク組成物に対する露光は、例えば、紫外線、エキシマレーザー光等の活性エネルギー線を照射して行われる。
現像処理を行う場合、現像後に加熱による乾燥等の方法により、現像液を十分に除去するのが好ましい。
また、前述の感光性インク組成物を用いて得られる硬化物は、耐屈曲性に優れ、折り曲げても割れにくいため、フレキシブルデバイスにおいて好適に用いられる。例えば、上記の硬化物からなる厚さ50nmのフィルムを、半径6mm、好ましくは半径2mmの円柱状のステンレス棒に巻き付けた場合に、割れが生じない。
(C1-1):ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド。
(C1-2):2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド
(C1-3):エチル(2,4,6-トリメチルベンゾイル)フェニルフォスフィネート
得られた感光性インク組成物の、25℃にて、E型粘度計を用いて測定した粘度を表1に記す。また、得られた感光性インク組成物を用いて形成された硬化膜の屈折率と、光透過性とを下記処方に従って測定した。屈折率の測定結果を表1に記す。
ガラス基板上にインクジェット装置を用いて、各実施例、比較例の感光性インク組成物を塗布した。その後、395nmのUV-LED露光機を用いて、露光量2J/cm2で塗布膜を露光して硬化させ、厚さ3μmの硬化膜を得た。その膜についてMetricon社製プリズムカプラを用いて光線波長550nmでの屈折率を評価した。
屈折率測定で製膜された膜の光線透過率を、大塚電子製MCPD透過率計を用いて測定した。測定された光透過率に基づいて、以下の基準に従い、各実施例、及び各比較例の感光性インク組成物を用いて形成された硬化物の光透過率を評価した。
◎:光透過率が96%以上である。
〇:光透過率が95%以上96%未満である。
△:光透過率が93%以上95%未満である。
×:光透過率が93%未満である。
Claims (16)
- 光重合性化合物(A)と、光重合開始剤(C)とを含み、溶剤(S)を含むか又は含まない感光性インク組成物であって、
前記光重合性化合物が、下記式(a-1)で表されるスルフィド化合物(A1)と、下記式(a-2)で表される(メタ)アクリレート化合物(A2)とを含み、
前記光重合開始剤(C)が、フォスフィンオキサイド化合物(C1)と、オキシムエステル化合物(C2)とを組み合わせて含む、感光性インク組成物。
- フォスフィンオキサイド化合物(C1)の質量W1とオキシムエステル化合物(C2)の質量W2との合計に対する、オキシムエステル化合物(C2)の質量W2の質量の比率が30質量%以上である、請求項1に記載の感光性インク組成物。
- オキシムエステル化合物(C2)が、吸光スペクトルにおいて、320nm以上400nm未満の波長域においてピークを有し、且つ、400nm以上の波長域のいずれかの波長において10以上のグラム吸光係数を示す化合物を含まない、請求項1又は2に記載の感光性インク組成物。
- 25℃にて、E型粘度計を用いて測定される粘度が40cP以下である、請求項1~4のいずれか1項に記載の感光性インク組成物。
- さらに、酸化ジルコニウム粒子、酸化チタン粒子、チタン酸バリウム粒子、酸化セリウム粒子、及び硫化亜鉛粒子からなる群より選択される1種以上の金属化合物粒子(B)を含む、請求項1~5のいずれか1項に記載の感光性インク組成物。
- 前記感光性インク組成物の前記溶媒(S)の質量を除いた質量に対する、前記金属化合物粒子(B)の質量の比率が、5質量%以上70質量%以下である、請求項6に記載の感光性インク組成物。
- 前記光重合性化合物(A)の質量に対する、前記スルフィド化合物(A1)の質量と、前記(メタ)アクリレート化合物(A2)の質量との合計の比率が80質量%以上である、請求項1~7のいずれか1項に記載の感光性インク組成物。
- 前記感光性インク組成物の前記溶媒(S)の質量を除いた質量に対する、前記スルフィド化合物(A1)の質量の比率が、5質量%以上30質量%以下である、請求項1~8のいずれか1項に記載の感光性インク組成物。
- 前記感光性インク組成物の前記溶媒(S)の質量を除いた質量に対する、前記(メタ)アクリレート化合物(A2)の質量の比率が、10質量%以上50質量%以下である、請求項1~9のいずれか1項に記載の感光性インク組成物。
- 請求項1~10のいずれか1項に記載の感光性インク組成物の硬化物。
- 屈折率が1.67以上である、請求項11に記載の硬化物。
- 請求項11又は12に記載の硬化物からなる膜を備える、ディスプレイパネル。
- 請求項1~10のいずれか1項に記載の感光性インク組成物を、形成される硬化物の形状に応じて成形することと、
成形された前記感光性インク組成物に対して露光することと、
を含む硬化物の製造方法。 - 前記感光性インク組成物が、塗布により膜状に成形される、請求項14に記載の硬化物の製造方法。
- 前記塗布がインクジェット印刷法により行われる、請求項15に記載の硬化物の製造方法。
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