TWI512395B - Photosensitive resin composition - Google Patents
Photosensitive resin composition Download PDFInfo
- Publication number
- TWI512395B TWI512395B TW098144798A TW98144798A TWI512395B TW I512395 B TWI512395 B TW I512395B TW 098144798 A TW098144798 A TW 098144798A TW 98144798 A TW98144798 A TW 98144798A TW I512395 B TWI512395 B TW I512395B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- methyl
- resin composition
- photosensitive resin
- dimethyl
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 67
- -1 aliphatic monocyclic compound Chemical class 0.000 claims description 346
- 150000001875 compounds Chemical class 0.000 claims description 76
- 239000002904 solvent Substances 0.000 claims description 71
- 238000000576 coating method Methods 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 39
- 239000004094 surface-active agent Substances 0.000 claims description 35
- 238000009835 boiling Methods 0.000 claims description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- 239000003505 polymerization initiator Substances 0.000 claims description 22
- 125000003700 epoxy group Chemical group 0.000 claims description 21
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 229920002098 polyfluorene Polymers 0.000 claims description 7
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 70
- 239000000203 mixture Substances 0.000 description 27
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 239000000470 constituent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 125000001931 aliphatic group Chemical group 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 8
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000003566 oxetanyl group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 150000007514 bases Chemical class 0.000 description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 6
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 6
- QYGBYAQGBVHMDD-XQRVVYSFSA-N (z)-2-cyano-3-thiophen-2-ylprop-2-enoic acid Chemical compound OC(=O)C(\C#N)=C/C1=CC=CS1 QYGBYAQGBVHMDD-XQRVVYSFSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical group CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 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 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
- 238000007607 die coating method Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 150000002923 oximes Chemical class 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 3
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- ONHGNKIAAHVLFS-UHFFFAOYSA-N B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])[O-].C1(=CC=C(C=C1)[I+]C1=CC=C(C=C1)C)C.C1(=CC=C(C=C1)[I+]C1=CC=C(C=C1)C)C Chemical compound B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])[O-].C1(=CC=C(C=C1)[I+]C1=CC=C(C=C1)C)C.C1(=CC=C(C=C1)[I+]C1=CC=C(C=C1)C)C ONHGNKIAAHVLFS-UHFFFAOYSA-N 0.000 description 3
- OULFEGDVEQMHCH-UHFFFAOYSA-N B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])[O-].C1(=CC=CC=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound B(OC1=C(C(=C(C(=C1F)F)F)F)F)([O-])[O-].C1(=CC=CC=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1 OULFEGDVEQMHCH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- IPTNXMGXEGQYSY-UHFFFAOYSA-N acetic acid;1-methoxybutan-1-ol Chemical compound CC(O)=O.CCCC(O)OC IPTNXMGXEGQYSY-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- CSCWNRYPJNQHQA-UHFFFAOYSA-N dioxido-(2,3,4,5,6-pentafluorophenoxy)borane;(4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound [O-]B([O-])OC1=C(F)C(F)=C(F)C(F)=C1F.C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1.C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 CSCWNRYPJNQHQA-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 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 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 125000004149 thio group Chemical group *S* 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QKAIFCSOWIMRJG-UHFFFAOYSA-N (4-methylphenyl)-(4-propan-2-ylphenyl)iodanium Chemical compound C1=CC(C(C)C)=CC=C1[I+]C1=CC=C(C)C=C1 QKAIFCSOWIMRJG-UHFFFAOYSA-N 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical group BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical group ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 2
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical group C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 2
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- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229960004599 sodium borate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- BZBMBZJUNPMEBD-UHFFFAOYSA-N tert-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC(C)(C)C)CC1C=C2 BZBMBZJUNPMEBD-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- 239000012953 triphenylsulfonium Substances 0.000 description 1
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
- Y10S430/106—Binder containing
- Y10S430/11—Vinyl alcohol polymer or derivative
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Optical Filters (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本發明係關於一種感光性樹脂組成物。
近年來之液晶顯示面板等已朝基板尺寸之大型化進行,通常,為了在基板面上形成塗層等之透明膜或圖型,係藉由旋轉塗佈法、狹縫及旋轉法等塗佈感光性樹脂組成物而形成。
另一方面,就提高生產性、對應於大型畫面等之觀點而言,己研究使感光性樹脂組成物溶液省液化並且形成高品質之均勻塗膜之方法。
基於該等背景,為了形成優異品質之塗膜而探討溶劑種類之選擇。例如,若使用低沸點溶劑,雖使塗膜之乾燥加速進行,但另一方面,溶劑蒸發時,有引起塗膜形成用組成物中所含微小氣泡突沸之情況。該等突沸會在塗膜表面上出現氣泡,亦帶來彈坑狀缺陷。
因此,自以往以來,係使用高沸點溶劑作為溶劑。例如,已提出有包含二乙二醇乙基甲基醚(沸點176℃)及苄基醇(沸點205℃)等高沸點溶劑之感光性樹脂組成物(例如,專利文獻1)。
專利文獻1:特開2007-25645號公報 第46段,表1
因此,使用上述高沸點溶劑之感光性樹脂組成物即使適用於以代表性塗佈方法的狹長模嘴塗佈法等,亦有無法獲得必定不發生霧狀斑點或缺陷等之高品質塗膜之情況。
本發明之目的為提供一種可形成因溶劑突沸引起之缺陷或霧狀斑點等之發生受到抑制、遍及塗膜全體為均勻之高品質塗膜之感光性樹脂組成物。
亦即,本發明為提供以下之[1]~[8]者。
[1]一種感光性樹脂組成物,其係包含樹脂(A)、聚合性單體(B)、聚合起始劑(C)、溶劑(D)及界面活性劑(E)之感光性樹脂組成物,其中溶劑(D)係包含兩種以上沸點為175℃以下之溶劑的溶劑,界面活性劑(E)之含量係相對於界面活性劑除外之感光性樹脂組成物100重量%而言為0.0025~0.0250重量%,且該感光性樹脂組成物之固形成分量為10~30重量%。
[2]如[1]所述之感光性樹脂組成物,其中溶劑(D)係包含兩種以上沸點為140℃以上175℃以下之溶劑的溶劑。
[3]如[1]或[2]所述之感光性樹脂組成物,其中溶劑(D)係包含碳數1~6之醇的溶劑。
[4]如[1]至[3]中任一項所述之感光性樹脂組成物,其中溶劑(D)係包含3-甲氧基丁醇之溶劑。
[5]如[1]至[4]中任一項所述之感光性樹脂組成物,其中界面活性劑(E)係選自由聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑所組成群組之至少一種。
[6]一種塗膜,其特徵為使用[1]至[5]中任一項所述之感光性樹脂組成物所形成。
[7]一種圖型,其特徵為使用[1]至[5]中任一項所述之感光性樹脂組成物所形成。
[8]一種顯示裝置,其特徵為包含[6]所述之塗膜及/或[7]所述之圖型。
本發明之感光性樹脂組成物主要包含樹脂(A)、聚合性單體(B)、聚合起始劑(C)、溶劑(D)及界面活性劑(E)。
本發明之感光性樹脂組成物中使用之樹脂(A)並無特別限制,較好為鹼溶解性者(A1),更好為因光及熱之至少一者之作用而顯示反應性者(A2)。
作為樹脂(A1)例示有選自由不飽和羧酸及不飽和羧酸酐所構成群組之至少一種(A-a)(以下有時稱為「(A-a)」)與可與(A-a)共聚合之單體(A-b)(但(A-a)除外)(以下有時稱為「(A-b)」)之共聚物等。
作為(A-a)列舉為例如脂肪族不飽和羧酸及/或脂肪族不飽和羧酸酐等,具體而列舉為下列者:丙烯酸、甲基丙烯酸、巴豆酸等不飽和單羧酸類;馬來酸、富馬酸、甲基馬來酸、仲康酸、衣康酸等不飽和二羧酸類;及該等不飽和二羧酸類之酸酐;琥珀酸單[2-(甲基)丙烯醯氧基乙酯]、苯二甲酸單[2-(甲基)丙烯醯氧基乙酯]等之二價以上之多價羧酸之不飽和單[(甲基)丙烯醯氧基烷酯]類;α-(羥基甲基)丙烯酸等之於同一分子中含有羥基及羧基之不飽和丙烯酸酯類等。
其中,就共聚合反應性及鹼溶解性之方面而言以丙烯酸、甲基丙烯酸或馬來酸酐等較佳。
該等可單獨使用亦可組合兩種以上使用。又,本說明書中只要沒有特別說明,則例示之化合物、成分、試劑等任一種均可單獨使用或組合兩種以上使用。
又本說明書中,所謂的「(甲基)丙烯酸」係表示選自由丙烯酸及甲基丙烯酸所組成群組之至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之表述亦具有相同意義。
至於(A-b)列舉為下列者:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯等之(甲基)丙烯酸烷酯類;(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02.6
]癸-8-基酯(於本技術領域中作慣用名稱係稱為(甲基)丙烯酸二環戊基酯)、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異冰片酯等之(甲基)丙烯酸環狀烷酯類;丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環[5.2.1.02.6
]癸-8-基酯(於本技術領域中作為慣用名稱係稱為丙烯酸二環戊基酯)、丙烯酸二環戊基氧基乙酯、丙烯酸異冰片酯等之丙烯酸環狀烷酯類;(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸芳酯類;丙烯酸苯酯、丙烯酸苄酯等丙烯酸芳酯類;馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等二羧酸二酯;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等之羥基烷酯類;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羧基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯酸酐(納迪克酸酐(Himic Anhydride))、5-第三丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己基氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-二(第三丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-二(環己基氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物類;N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺基-6-馬來醯亞胺己酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等之二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊間二烯、2,3-二甲基-1,3-丁二烯等。
其中,就共聚合反應性及鹼溶解性之方面而言以苯乙烯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、雙環[2.2.1]庚-2-烯等較佳。
使(A-a)及(A-b)共聚合獲得之樹脂(A1),由各別所誘導出之構成成分之比率,以構成樹脂(A1)之構成成分之總莫耳數作為100莫耳%時之莫耳分率計,較好在以下之範圍:
由(A-a)誘導出之構成單位:2~40莫耳%
由(A-b)誘導出之構成單位:60~98莫耳%
又,前述構成成分之比率更好在以下範圍:
由(A-a)誘導出之構成單位:5~35莫耳%
由(A-b)誘導出之構成單位:65~95莫耳%
若前述之構成比率在該範圍內,有儲存安定性、顯像性及耐溶劑性變得良好之傾向。
樹脂(A1)可參考例如文獻「高分子合成之實驗法」(大津隆行著 化學同人(股)發行所 第1版第1刷 1972年3月1日發行)所述之方法及該文獻中所述之引用文獻加以製造(樹脂(A2)時亦同)。
具體而言,將構成共聚物之單位(A-a)及(A-b)特定量、聚合起始劑及溶劑饋入反應容器中,以氮氣置換氧氣,在沒有氧存在下藉由攪拌、加熱、保溫,獲得聚合物。
此處所用之聚合起始劑可使用該技術領域中通常使用之任一種。例如可使用後述之聚合起始劑(C)等。
又,所得共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用以再沉澱等方法作為固體(粉體)而取出者。
尤其,藉由使用後述之溶劑(D)作為該聚合時之溶劑,反應後之溶液可直接被使用,而可簡化製造步驟(樹脂(A2)時亦同)。
樹脂(A1)之聚苯乙烯換算之重量平均分子量較好為3,000~100,000,更好為5,000~50,000。樹脂(A1)之重量平均分子量在該範圍時,有塗佈性成為良好之傾向,又,顯像時不易產生膜減少,進而有顯像時非像素部份之脫落性良好之傾向。
樹脂(A1)之分散度(分子量分佈)、[重量平均分子量(Mw)/數平均分子量(Mn)]較好為1.1~6.0,更好為1.2~4.0。分散度在該範圍時,有顯像性優異之傾向。
可用於本發明之感光性樹脂組成物中之樹脂(A1)之含量相對於感光性樹脂組成物中之固形成分之質量分率較好為5~90質量%,更好為10~70質量%。樹脂(A1)之含量在該範圍內時,成為對顯像液之溶解性充分,不易在非像素部份之基板上發生顯像殘渣,又顯像時之曝光部份之像素部份不易產生膜減少,而有非曝光部份之脫落性良好之傾向。
鹼溶解性及利用光及熱之至少一種之作用而顯示反應性之樹脂(A2)例示為(A2-1)~(A2-3)。
樹脂(A2-1)列舉為(A-a)、(A-b)及具有含有碳數2~4之環狀醚鍵之基之單體(A-c)(以下有時稱為「(A-c)」)之共聚物。
樹脂(A2-2)列舉為在(A-a)及(A-b)之共聚物中,使源自(A-a)之羧基之一部分與源自(A-c)之具有碳數2~4之環狀醚鍵之基反應獲得之共聚物。
樹脂(A2-3)列舉為(A-a)與(A-c)之共聚物。
(A-c)係指具有選自由例如具有碳數2~4之環狀醚鍵之基(例如環氧基、氧雜環丁烷基及四氫呋喃基)所構成之群組之至少一種基之聚合性化合物。(A-c)較好為具有選自由具有碳數2~4之環狀醚鍵之基所構成之群組之至少一種基且具有不飽和鍵之化合物。
至於(A-c)列舉為例如具有環氧基之單體、具有氧雜環丁烷基之單體、具有四氫呋喃基之單體等。
前述具有環氧基之單體係指例如具有選自由脂肪族環氧基及脂環式環氧基所構成群組之至少一種基之聚合性化合物。
具有環氧基之單體較好為具有選自由脂肪族環氧基及脂環式環氧基所構成群組之至少一種基且具有不飽和鍵之化合物。
所謂脂肪族環氧基係指具有使鏈式烯烴之環氧化之構造之基。
具有脂肪族環氧基之化合物具體而言舉例為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油基乙烯基醚、特開平7-248625號公報中所述之以下述式(III)表示之化合物等:
(式(III)中,R11
~R13
各獨立為氫原子或碳原子數1~10之烷基,m為1~5之整數)。
其中,烷基例示為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、1-甲基-正丙基、2-甲基-正丙基、第三丁基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、正己基、環己基等。
又,任一化學構造式雖依據碳數而有不同,但只要沒有特別說明,則取代基等之例示可同樣地適用於本說明書全部。又,可具有直鏈或分支二種者,亦包含其任一種。
以前述式(III)表示之化合物列舉為例如鄰-乙烯基苄基縮水甘油醚、間-乙烯基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚、α-甲基-鄰-乙烯基苄基縮水甘油醚、α-甲基-間-乙烯基苄基縮水甘油醚、α-甲基-對-乙烯基苄基縮水甘油醚、2,3-二縮水甘油氧基甲基苯乙烯、2,4-二縮水甘油氧基甲基苯乙烯、2,5-二縮水甘油氧基甲基苯乙烯、2,6-二縮水甘油氧基甲基苯乙烯、2,3,4-三縮水甘油氧基甲基苯乙烯、2,3,5-三縮水甘油氧基甲基苯乙烯、2,3,6-三縮水甘油氧基甲基苯乙烯、3,4,5-三縮水甘油氧基甲基苯乙烯、2,4,6-三縮水甘油氧基甲基苯乙烯等。
具有脂環式環氧基之單體列舉為例如具有脂肪族單環式環氧基之單體、具有脂肪族多環式環氧基之單體。
所謂脂環式環氧基係指帶有使環式烯烴環氧化之構造之基者。又,所謂脂環族單環式環氧基係指帶有使單環之環式烯烴環氧化之構造之基者,所謂脂肪族多環式環氧基係指帶有使多環之環式烯烴環氧化之構造之基者。
前述具有脂肪族單環式環氧基之單體係指脂肪族單環式化合物之環上具有環氧基之聚合性化合物。具有脂肪族單環式環氧基之單體較好為脂肪族單環式化合物之環上具有環氧基且具有不飽和鍵之化合物,更好為於脂肪族單環式化合物之環上具有環氧基且具有(甲基)丙烯醯氧基之化合物。
脂肪族單環式化合物列舉為例如環戊烷、環己烷、環庚烷、環辛烷等。其中,以碳數5~7之化合物較佳。
具有脂肪族單環式環氧基之單體,具體而言列舉為乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如,CELLOXIDE 2000;Daicel化學工業(股)製造)、3,4-環氧基環己基甲基丙烯酸酯(例如,CYCLMER A400,Daicel化學工業(股)製造)、3,4-環氧基環己基甲基甲基丙烯酸酯(例如,CYCLMER M100,Daicel化學工業(股)製造)等。
前述具有脂肪族多環式環氧基之單體係指脂肪族多環式化合物之環上具有環氧基之聚合性化合物。具有脂肪族多環式環氧基之單體較好為脂肪族多環式化合物之環上具有環氧基且具有不飽和鍵者,更好為脂肪族多環式化合物之環上具有環氧基且具有(甲基)丙烯醯氧基之化合物。
至於脂肪族多環式化合物列舉為例如二環戊烷、三環癸烷、原冰片烷、異原冰片烷、雙環辛烷、雙環壬烷、雙環十一碳烷、三環十一碳烷、雙環十二碳烷、三環十二碳烷等。其中,以碳數8~12之化合物較佳。
前述具有脂肪族多環式環氧基之單體列舉為例如3,4-環氧基原冰片基丙烯酸酯、3,4-環氧基原冰片基甲基丙烯酸酯、選自由以式(I)表示之化合物及以式(II)表示之化合物所構成群組之至少一種化合物等。
式(I)及式(II)中,R1
及R2
各獨立表示氫原子或可經羥基取代之碳數1~4之烷基。
X1
及X2
各獨立表示單鍵或可含雜原子之碳數1~6之伸烷基。
R1
及R2
具體而言列舉為氫原子;甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等烷基;羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基-正丙基、2-羥基-正丙基、3-羥基-正丙基、1-羥基-異丙基、2-羥基-異丙基、1-羥基-正丁基、2-羥基-正丁基、3-羥基-正丁基、4-羥基-正丁基等之羥基取代之烷基。
較好為氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基,更好為氫原子、甲基。
X1
及X2
具體而言列舉為單鍵;伸甲基、伸乙基、伸丙基等伸烷基;氧基伸烷基、硫伸烷基、胺基伸烷基等含有雜原子之伸烷基,具體而言例示為氧基伸甲基、氧基伸乙基、氧基伸丙基、硫基伸甲基、硫基伸乙基、硫基伸丙基、胺基伸甲基、胺基伸乙基、胺基伸丙基等。
較好列舉為單鍵、伸甲基、伸乙基、氧基伸甲基、氧基伸乙基,更好列舉為單鍵、氧基伸乙基。
選自由以式(I)表示之化合物及以式(II)表示之化合物所構成群組之至少一種化合物較好為選自由以下述式(I’)表示之化合物及以式(II’)表示之化合物所構成群組之至少一種化合物:
式(I’)及式(II’)中,R1’
及R2’
分別與前述R1
及R2
相同意義。
以式(I)表示之化合物具體而言列舉為以式(I-1)~式(I-15)表示之化合物等,較好列舉為式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)、式(I-11)~式(I-15),更好列舉為式(I-1)、式(I-7)、式(I-9)、式(I-15)。
以式(II)表示之化合物具體而言列舉為以式(II-1)~式(II-15)表示之化合物等,較佳列舉為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)、式(II-11)~式(II-15),更好者列舉為式(II-1)、式(II-7)、式(II-9)、式(II-15)。
選自由以式(I)表示之化合物及以式(II)表示之化合物所組成群組之至少一種化合物可個別單獨使用,亦可以任意之比率混合使用。混合時,其混合比率以莫耳比計較好為式(I):式(II)為5:95~95:5,更好為10:90~90:10,又更好為20:80~80:20。
前述具有氧雜環丁烷基之單體係指例如具有氧雜環丁烷之聚合性化合物。具有氧雜環丁烷基之單體較佳為具有氧雜環丁烷基且具有不飽和鍵之化合物。
具有氧雜環丁烷基之單體具體而言列舉為3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷或3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。
前述具有四氫呋喃基之單體係指例如具有四氫呋喃基之聚合性化合物。具有四氫呋喃基之單體較好為具有四氫呋喃基且具有不飽和鍵之化合物。
具有四氫呋喃基之單體具體而言列舉為丙烯酸四氫糠酯(例如,VISCOAT V#150,大阪有機化學工業(股)製造)、甲基丙烯酸四氫糠酯等。
樹脂(A2-1)中,由各自所誘導之構成成分之比率相對於構成樹脂(A2-1)之構成成分之合計莫耳數,莫耳分率計,較好在以下之範圍:
由(A-a)誘導之構成單位;2~40莫耳%
由(A-b)誘導之構成單位;1~65莫耳%
由(A-c)誘導之構成單位;2~95莫耳%
另外,前述構成成分之比率若在以下範圍內則更好:
由(A-a)誘導之構成單位;5~35莫耳%
由(A-b)誘導之構成單位;1~60莫耳%
由(A-c)誘導之構成單位;5~80莫耳%
前述之構成比率若在該範圍內,則有儲存安定性、顯像性、耐溶劑性、耐熱性及機械強度成為良好之傾向。
樹脂(A2-1)除使用誘導出構成共聚物之單位(A-a)、(A-b)及(A-c)之化合物以外,可利用與樹脂(A1)相同之製造方法製造。
樹脂(A2-2)可經二階段之步驟製造。例如可參考文獻「高分子合成之實驗法」(大津隆行著化學同人(股)發行所第1版第1刷1972年3月1日發行)所述之方法,或特開2001-89533號公報中所述之方法製造。
首先,使用使(A-a)及(A-b)共聚合獲得之共聚物,利用與樹脂(A1)相同之方法獲得樹脂。
該情況下,由各個所誘導之構成成分之比率,以相對於構成前述共聚物之構成成分之總莫耳數之莫耳分率計,較好在以下之範圍。
由(A-a)誘導之構成單位;5~50莫耳%
由(A-b)誘導之構成單位;50~95莫耳%
又,前述之構成成分之比率若在以下之範圍內則更好:
由(A-a)誘導之構成單位;10~45莫耳%
由(A-b)誘導之構成單位;55~90莫耳%
所得樹脂之聚苯乙烯換算重量平均分子量、分子量分佈[重量平均分子量(Mw)/數平均分子量(Mn)]可為與樹脂(A1)相同之程度。
接著,為了賦予因光或熱作用之反應性,使源自使(A-a)及(A-b)共聚合獲得之共聚物之(A-a)之羧酸及羧酸酐之一部分與源自(A-c)之環氧基、氧雜環丁烷基或四氫呋喃基反應。
據此,接著將燒瓶內之氛圍氣體由氮氣置換成空氣,且將構成成分(A-c)、反應觸媒及聚合抑制劑等置入燒瓶內,在例如60~130℃下繼續反應1~10小時。
又,與聚合條件同樣,可考慮製造設備或因聚合產生之發熱量等,而適度調整饋入方法或反應溫度。
(A-c)之莫耳數相對於(A-a)之莫耳數通常為5~80莫耳%,較好為10~75莫耳%,更好為15~70莫耳%。構成比率在該範圍內時,有儲存安定性、顯像性、耐溶劑性、耐熱性、機械強度及感度之均衡成為良好之傾向。
反應觸媒以例如羧基與環氧基、氧雜環丁烷基或四氫呋喃基之作為反應觸媒使用者。具體而言,例示為叁二甲胺基甲基酚等。
該情況下之反應觸媒使用量通常相對於單體(A-a)~(A-c)之合計量,以質量基準為0.001~5%左右。
聚合抑制劑例示為氫醌。
聚合抑制劑之使用量通常相對於單體(A-a)~(A-c)之合計量,以質量基準為0.001~5%左右。
樹脂(A2-3)除使用誘導出構成共聚物之單位(A-a)及(A-c)之化合物以外,可利用與樹脂(A1)相同之製造方法製造。
樹脂(A2-3)中,由各個所誘導之構成成分之比率,相對於構成樹脂(A2-3)之構成成分之合計莫耳數之莫耳分率計,較好在以下之範圍:
由(A-a)誘導之構成單位;5~95莫耳%
由(A-c)誘導之構成單位;5~95莫耳%
又,前述構成成分之比率若在以下範圍內更好:
由(A-a)誘導之構成單位;10~90莫耳%
由(A-c)誘導之構成單位;10~90莫耳%
前述之構成比率若在該範圍內,則有儲存安定性、顯像性、耐溶劑性、耐熱性及機械強度成為良好之傾向。
本發明之感光性樹脂組成物中所含聚合性單體(B)列舉為單官能基單體、二官能基單體或三官能基以上之多官能基單體。
單官能基單體列舉為(甲基)丙烯酸壬基苯基卡必醇酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸2-乙基己基卡必醇酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸己內酯、(甲基)丙烯酸乙氧基化壬基酚酯、(甲基)丙烯酸丙氧化壬基酚酯或N-乙烯基吡咯啶酮等。
二官能基單體列舉為1,3-丁二醇二(甲基)丙烯酸酯、1,3-丁二醇(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二丙烯酸酯、雙酚A之雙(丙烯醯氧基乙基)醚、乙氧化雙酚A二(甲基)丙烯酸酯、丙氧化新戊二醇二(甲基)丙烯酸酯、乙氧化新戊二醇二(甲基)丙烯酸酯或3-甲基戊二醇二(甲基)丙烯酸酯等。
三官能基以上之多官能基單體列舉為三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、叁(2-羥基乙基)異脲氰酸酯三(甲基)丙烯酸酯、乙氧化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇四(甲基)丙烯酸酯、三季戊四醇五(甲基)丙烯酸酯、三季戊四醇六(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、五季戊四醇三(甲基)丙烯酸酯與酸酐之反應物、二季戊四醇五(甲基)丙烯酸酯與酸酐之反應物、三季戊四醇七(甲基)丙烯酸酯與酸酐之反應物、己內酯改質三羥甲基丙烷三(甲基)丙烯酸酯、己內酯改質季戊四醇三(甲基)丙烯酸酯、己內酯改質叁(2-羥基乙基)異脲氰酸酯三(甲基)丙烯酸酯、己內酯改質季戊四醇四(甲基)丙烯酸酯、己內酯改質二季戊四醇五(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯、己內酯改質三季戊四醇四(甲基)丙烯酸酯、己內酯改質三季戊四醇五(甲基)丙烯酸酯、己內酯改質三季戊四醇六(甲基)丙烯酸酯、己內酯改質三季戊四醇七(甲基)丙烯酸酯、己內酯改質三季戊四醇八(甲基)丙烯酸酯、己內酯改質季戊四醇三(甲基)丙烯酸酯與酸酐之反應物、己內酯改質二季戊四醇五(甲基)丙烯酸酯與酸酐之反應物、或己內酯改質三季戊四醇七(甲基)丙烯酸酯與酸酐之反應物等。
又,本說明書中,所謂的己內酯改質意指(甲基)丙烯酸酯化合物之源自醇部位與(甲基)丙烯醯氧基之間導入己內酯之開環物或開環聚合物。
其中,較好使用二官能基以上之多官能基單體。
聚合性單體(B)之含量,以相對於樹脂(A)及聚合性單體(B)之合計量之質量分率計,較好為1~70質量%,更好為5~60質量%。聚合性單體(B)之含量在該範圍內時,有感度、塗膜及圖型之強度、平滑性、信賴性及機械強度成為良好之傾向。
本發明之感光性樹脂組成物亦可進而含有選自由羧酸酐及具有至少兩個羧基之化合物所組成群組之至少一種化合物(Y)。後者之化合物可列舉為例如多價羧酸酐、多價羧酸等。
至於羧酸酐亦可適當地使用由市售之無色酸酐所成之環氧樹脂硬化劑。具體而言列舉為ADEKA HARDNER EH-700(商品名(以下相同),旭電化工業(股)製造)、RIKACID-HH、RIKACID-MH-700(新日本理化(股)製造)、EPICURE 126、EPICURE YH-306、EPICURE DX-126(油化Shell Epoxy(股)製造)等。
至於多價羧酸酐列舉為例如下列者:衣康酸酐、琥珀酸酐、仲康酸酐、十二碳烯基琥珀酸酐、三羧酸酐、馬來酸酐、六氫苯二甲酸酐、甲基四氫苯二甲酸酐、原冰片烯二羧酸、納迪克酸酐等之脂肪族二羧酸酐;1,2,3,4-丁烷四羧酸二酐、環戊烷四羧酸二酐等之脂肪族多價羧酸二酐;苯二甲酸酐、均苯四酸酐、偏苯三酸酐、二苯甲酮四羧酸酐等之芳香族多價羧酸酐;乙二醇雙偏苯三酸酯、丙三醇叁偏苯三酸酯等含有酯基之酸酐等。
其中,就透明性高、解像度高之方面而言較好為苯二甲酸酐、偏苯三酸酐。
至於多價羧酸列舉為例如下列者:琥珀酸、戊二酸、己二酸、丁烷四羧酸、馬來酸、衣康酸等之脂肪族多價羧酸;六氫苯二甲酸、1,2-環己烷羧酸、1,2,4-環己烷三羧酸、環戊烷四羧酸等之脂肪族多價羧酸;苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三酸、均苯四酸、1,4,5,8-萘四羧酸、二苯甲酮四羧酸等之芳香族多價羧酸等。
其中,就透明性高、解像度高之方面而言,較好為苯二甲酸、偏苯三酸。
本發明之感光性樹脂組成物中之化合物(Y)之含量,以相對於黏合劑樹脂(A)及聚合性單體(B)之合計量之質量分率計,較好為0.1~20質量%,更好為1~15質量%。化合物(Y)落在該範圍內時,可提高解像度及殘膜率。
本發明之感光性樹脂組成物中所含聚合起始劑(C)列舉為藉由光或熱之作用開始聚合之化合物,舉例為例如雙咪唑系化合物、苯乙酮系化合物、三嗪系化合物、醯基氧化膦系化合物或肟系化合物等。其中,雙咪唑系化合物由於感度優異故而較佳。
雙咪唑化合物列舉為2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑(例如,參照特開平6-75372號公報,特開平6-75373號公報等),2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)雙咪唑(例如,參照特公昭48-38403號公報,特開昭62-174204號公報等)、4,4’,5,5’-位之苯基經碳烷氧基取代而得之咪唑化合物(例如,參照特開平7-10913號公報等)等。
較好列舉為2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基雙咪唑。
苯乙酮系化合物列舉為二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、苄基二甲基縮酮、2-羥基-1-[4-(2-羥基乙氧基)苯基]-2-甲基丙-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]-苯基}-2-甲基-丙-1-酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲基硫烷基(sulfanyl)苯基)-2-嗎啉基丙-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)丁-1-酮、2-(2-甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-乙基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-丙基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-丁基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2,3-二甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2,4-二甲基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-氯苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-溴苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-氯苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-氯苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-溴苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-溴苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲氧基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(3-甲氧基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(4-甲氧基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲基-4-甲氧基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-甲基-4-溴苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-(2-溴-4-甲氧基苄基)-2-二甲胺基-1-(4-嗎啉基苯基)-丁酮、2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙-1-酮之寡聚物等。
三嗪系化合物列舉為2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。
醯基氧化膦系起始劑列舉為2,4,6-三甲基苯甲醯基二苯基氧化膦等。
肟化合物列舉為O-乙氧基羰基-α-氧亞胺基-1-苯基丙-1-酮、以式(1)表示之化合物、以式(2)表示之化合物等。
本發明之感光性樹脂組成物之聚合起始劑(C)亦可包含以下之光聚合起始劑。
光聚合起始劑列舉為例如苯偶因系化合物、二苯甲酮系化合物或噻噸酮系化合物等。
苯偶因系化合物列舉為例如苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚及苯偶因異丁基醚等。
二苯甲酮系化合物列舉為例如二苯甲酮、鄰-苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫醚、3,3’,4,4’-四(第三丁基過氧基羰基)二苯甲酮及2,4,6-三甲基二苯甲酮等。
噻噸酮系化合物列舉為例如2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮等。
再者、亦可使用10-丁基-2-氯吖啶酮、2-乙基蒽醌、苄基、9,10-菲醌、樟腦醌、苯基乙醛酸甲酯或二茂鈦(titanocene)化合物等作為光聚合起始劑。
又,具有引發鏈轉移之基之光聚合起始劑可使用特表2002-544205號公報中所述之光聚合起始劑。
前述具有引發鏈轉移之基之光聚合起始劑列舉為例如以下述式(3)至下述式(8)之光聚合起始劑。
又,可使用光及/或熱陽離子聚合起始劑。
光及/或熱陽離子聚合起始劑亦可使用由鎓陽離子與源自路易斯酸之陰離子所構成者。
鎓陽離子之具體例列舉為二苯基碘鎓、雙(對-甲苯基)碘鎓、雙(對-第三丁基苯基)碘鎓、雙(對-辛基苯基)碘鎓、雙(對-十八烷基苯基)碘鎓、雙(對-辛氧基苯基)碘鎓、雙(對-十八烷基氧基苯基)碘鎓、苯基(對-十八烷基氧基苯基)碘鎓、(對-甲苯基)(對-異丙基苯基)碘鎓、三苯基鋶、叁(對-甲苯基)鋶、叁(對-異丙基苯基)鋶、叁(2,6-二甲基苯基)鋶、叁(對-第三丁基苯基)鋶、叁(對-氰基苯基)鋶、叁(對-氯苯基)鋶、二甲基(甲氧基)鋶、二甲基(乙氧基)鋶、二甲基(丙氧基)鋶、二甲基(丁氧基)鋶、二甲基(辛氧基)鋶、二甲基(十八烷基氧基)鋶、二甲基(異丙氧基)鋶、二甲基(第三丁氧基)鋶、二甲基(環戊基氧基)鋶、二甲基(環己基氧基)鋶、二甲基(氟甲氧基)鋶、二甲基(2-氯乙氧基)鋶、二甲基(3-溴丙氧基)鋶、二甲基(4-氰基丁氧基)鋶、二甲基(8-硝基辛氧基)鋶、二甲基(18-三氟甲基十八烷基氧基)鋶、二甲基(2-羥基異丙氧基)鋶、或二甲基(叁(三氯甲基)甲基)鋶等。
較佳之鎓陽離子列舉為雙(對-甲苯基)碘鎓、(對-甲苯基)(對-異丙基苯基)碘鎓、雙(對-第三丁基苯基)碘鎓、三苯基鋶或叁(對-第三丁基苯基)鋶等。
源自上述路易絲酸之陰離子之具體例列舉為六氟磷酸根、六氟砷酸根、六氟銻酸根或肆(五氟苯基)硼酸根等。
較佳之源自路易絲酸之陰離子列舉為六氟銻酸根或肆(五氟苯基)硼酸根。
該等鎓陽離子及源自路易絲酸之陰離子可任意組合。
陽離子聚合起始劑之具體例列舉為二苯基碘鎓六氟磷酸鹽、雙(對-甲苯基)碘鎓六氟磷酸鹽、雙(對-第三丁基苯基)碘鎓六氟磷酸鹽、雙(對-辛基苯基)碘鎓六氟磷酸鹽、雙(對-十八烷基苯基)碘鎓六氟磷酸鹽、雙(對-辛基氧基苯基)碘鎓六氟磷酸鹽、雙(對-十八烷基氧基苯基)碘鎓六氟磷酸鹽、苯基(對-十八烷基氧基苯基)碘鎓六氟磷酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟磷酸鹽、甲基萘基碘鎓六氟磷酸鹽、乙基萘基碘鎓六氟磷酸鹽、三苯基鋶六氟磷酸鹽、叁(對-甲苯基)鋶六氟磷酸鹽、叁(對-異丙基苯基)鋶六氟磷酸鹽、叁(2,6-二甲基苯基)鋶六氟磷酸鹽、叁(對-第三丁基苯基)鋶六氟磷酸鹽、叁(對-氰基苯基)鋶六氟磷酸鹽、叁(對-氯苯基)鋶六氟磷酸鹽、二甲基萘基鋶六氟磷酸鹽、二乙基萘基鋶六氟磷酸鹽、二甲基(甲氧基)鋶六氟磷酸鹽、二甲基(乙氧基)鋶六氟磷酸鹽、二甲基(丙氧基)鋶六氟磷酸鹽、二甲基(丁氧基)鋶六氟磷酸鹽、二甲基(辛氧基)鋶六氟磷酸鹽、二甲基(十八烷基氧基)鋶六氟磷酸鹽、二甲基(異丙氧基)鋶六氟磷酸鹽、二甲基(第三丁氧基)鋶六氟磷酸鹽、二甲基(環戊基氧基)鋶六氟磷酸鹽、二甲基(環己基氧基)鋶六氟磷酸鹽、二甲基(氟甲氧基)鋶六氟磷酸鹽、二甲基(2-氯乙氧基)鋶六氟磷酸鹽、二甲基(3-溴丙氧基)鋶六氟磷酸鹽、二甲基(4-氰基丁氧基)鋶六氟磷酸鹽、二甲基(8-硝基辛氧基)鋶六氟磷酸鹽、二甲基(18-三氟甲基十八烷基氧基)鋶六氟磷酸鹽、二甲基(2-羥基異丙氧基)鋶六氟磷酸鹽、二甲基(叁(三氯甲基)甲基)鋶六氟磷酸鹽等;二苯基碘鎓六氟砷酸鹽、雙(對-甲苯基)碘鎓六氟砷酸鹽、雙(對-第三丁基苯基)碘鎓六氟砷酸鹽、雙(對-辛基苯基)碘鎓六氟砷酸鹽、雙(對-十八烷基苯基)碘鎓六氟砷酸鹽、雙(對-辛基氧基苯基)碘鎓六氟砷酸鹽、雙(對-十八烷基氧基苯基)碘鎓六氟砷酸鹽、苯基(對-十八烷基氧基苯基)碘鎓六氟砷酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟砷酸鹽、甲基萘基碘鎓六氟砷酸鹽、乙基萘基碘鎓六氟砷酸鹽、三苯基鋶六氟砷酸鹽、叁(對-甲苯基)鋶六氟砷酸鹽、叁(對-異丙基苯基)鋶六氟砷酸鹽、叁(2,6-二甲基苯基)鋶六氟砷酸鹽、叁(對-第三丁基苯基)鋶六氟砷酸鹽、叁(對-氰基苯基)鋶六氟砷酸鹽、叁(對-氯苯基)鋶六氟砷酸鹽、二甲基萘基鋶六氟砷酸鹽、二乙基萘基鋶六氟砷酸鹽、二甲基(甲氧基)鋶六氟砷酸鹽、二甲基(乙氧基)鋶六氟砷酸鹽、二甲基(丙氧基)鋶六氟砷酸鹽、二甲基(丁氧基)鋶六氟砷酸鹽、二甲基(辛氧基)鋶六氟砷酸鹽、二甲基(十八烷基氧基)鋶六氟砷酸鹽、二甲基(異丙氧基)鋶六氟砷酸鹽、二甲基(第三丁氧基)鋶六氟砷酸鹽、二甲基(環戊基氧基)鋶六氟砷酸鹽、二甲基(環己基氧基)鋶六氟砷酸鹽、二甲基(氟甲氧基)鋶六氟砷酸鹽、二甲基(2-氯乙氧基)鋶六氟砷酸鹽、二甲基(3-溴丙氧基)鋶六氟砷酸鹽、二甲基(4-氰基丁氧基)鋶六氟砷酸鹽、二甲基(8-硝基辛氧基)鋶六氟砷酸鹽、二甲基(18-三氟甲基十八烷基氧基)鋶六氟砷酸鹽、二甲基(2-羥基異丙氧基)鋶六氟砷酸鹽、二甲基(叁(三氯甲基)甲基)鋶砷酸鹽等;二苯基碘鎓六氟銻酸鹽、雙(對-甲苯基)碘鎓六氟銻酸鹽、雙(對-第三丁基苯基)碘鎓六氟銻酸鹽、雙(對-辛基苯基)碘鎓六氟銻酸鹽、雙(對-十八烷基苯基)碘鎓六氟銻酸鹽、雙(對-辛基氧基苯基)碘鎓六氟銻酸鹽、雙(對-十八烷基氧基苯基)碘鎓六氟銻酸鹽、苯基(對-十八烷基氧基苯基)碘鎓六氟銻酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟銻酸鹽、甲基萘基碘鎓六氟銻酸鹽、乙基萘基碘鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、叁(對-甲苯基)鋶六氟銻酸鹽、叁(對-異丙基苯基)鋶六氟銻酸鹽、叁(2,6-二甲基苯基)鋶六氟銻酸鹽、叁(對-第三丁基苯基)鋶六氟銻酸鹽、叁(對-氰基苯基)鋶六氟銻酸鹽、叁(對-氯苯基)鋶六氟銻酸鹽、二甲基萘基鋶六氟銻酸鹽、二乙基萘基鋶六氟銻酸鹽、二甲基(甲氧基)鋶六氟銻酸鹽、二甲基(乙氧基)鋶六氟銻酸鹽、二甲基(丙氧基)鋶六氟銻酸鹽、二甲基(丁氧基)鋶六氟銻酸鹽、二甲基(辛氧基)鋶六氟銻酸鹽、二甲基(十八烷基氧基)鋶六氟銻酸鹽、二甲基(異丙氧基)鋶六氟銻酸鹽、二甲基(第三丁氧基)鋶六氟銻酸鹽、二甲基(環戊基氧基)鋶六氟銻酸鹽、二甲基(環己基氧基)鋶六氟銻酸鹽、二甲基(氟甲氧基)鋶六氟銻酸鹽、二甲基(2-氯乙氧基)鋶六氟銻酸鹽、二甲基(3-溴丙氧基)鋶六氟銻酸鹽、二甲基(4-氰基丁氧基)鋶六氟銻酸鹽、二甲基(8-硝基辛氧基)鋶六氟銻酸鹽、二甲基(18-三氟甲基十八烷基氧基)鋶六氟銻酸鹽、二甲基(2-羥基異丙氧基)鋶六氟銻酸鹽、二甲基(叁(三氯甲基)甲基)鋶六氟銻酸鹽等;二苯基碘鎓肆(五氟苯基)硼酸鹽、雙(對-甲苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-第三丁基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-辛基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-十八烷基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-辛基氧基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-十八烷基氧基苯基)碘鎓肆(五氟苯基)硼酸鹽、苯基(對-十八烷基氧基苯基)碘鎓肆(五氟苯基)硼酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓肆(五氟苯基)硼酸鹽、甲基萘基碘鎓肆(五氟苯基)硼酸鹽、乙基萘基碘鎓肆(五氟苯基)硼酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、叁(對-甲苯基)鋶肆(五氟苯基)硼酸鹽、叁(對-異丙基苯基)鋶肆(五氟苯基)硼酸鹽、叁(2,6-二甲基苯基)鋶肆(五氟苯基)硼酸鹽、叁(對-第三丁基苯基)鋶肆(五氟苯基)硼酸鹽、叁(對-氰基苯基)鋶肆(五氟苯基)硼酸鹽、叁(對-氯苯基)鋶肆(五氟苯基)硼酸鹽、二甲基萘基鋶肆(五氟苯基)硼酸鹽、二乙基萘基鋶肆(五氟苯基)硼酸鹽、二甲基(甲氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(乙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(辛氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(十八烷基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(異丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(第三丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(環戊基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(環己基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(氟甲氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(2-氯乙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(3-溴丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(4-氰基丁氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(8-硝基辛氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(18-三氟甲基十八烷基氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(2-羥基異丙氧基)鋶肆(五氟苯基)硼酸鹽、二甲基(叁(三氯甲基)甲基)鋶肆(五氟苯基)硼酸鹽等。
較佳者列舉為雙(對-甲苯基)碘鎓六氟磷酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟磷酸鹽、雙(對-第三丁基苯基)碘鎓六氟磷酸鹽、三苯基鋶六氟磷酸鹽、叁(對-第三丁基苯基)鋶六氟磷酸鹽、雙(對-甲苯基)碘鎓六氟砷酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟砷酸鹽、雙(對-第三丁基苯基)碘鎓六氟砷酸鹽、三苯基鋶六氟砷酸鹽、叁(對-第三丁基苯基)鋶六氟砷酸鹽、雙(對-甲苯基)碘鎓六氟銻酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟銻酸鹽、雙(對-第三丁基苯基)碘鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、叁(對-第三丁基苯基)鋶六氟銻酸鹽、雙(對-甲苯基)碘鎓肆(五氟苯基)硼酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-第三丁基苯基)碘鎓肆(五氟苯基)硼酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、叁(對-第三丁基苯基)鋶肆(五氟苯基)硼酸鹽等。
更佳者列舉為雙(對-甲苯基)碘鎓六氟銻酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓六氟銻酸鹽、雙(對-第三丁基苯基)碘鎓六氟銻酸鹽、三苯基鋶六氟銻酸鹽、叁(對-第三丁基苯基)鋶六氟銻酸鹽、雙(對-甲苯基)碘鎓肆(五氟苯基)硼酸鹽、(對-甲苯基)(對-異丙基苯基)碘鎓肆(五氟苯基)硼酸鹽、雙(對-第三丁基苯基)碘鎓肆(五氟苯基)硼酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、叁(對-第三丁基苯基)鋶肆(五氟苯基)硼酸鹽等。
聚合起始劑(C)之含量,以相對於樹脂(A)及聚合性單體(B)合計量之質量分率計,較好為0.1~40質量%,更好為1~30質量%。
聚合起始劑(C)之合計量在該範圍內時,有感光性樹脂組成物成為高感度,且使用前述感光性樹脂組成物形成之塗膜或圖型之強度,或前述塗膜或圖型之表面平滑性成為良好之傾向。
又,本發明之感光性樹脂組成物在不損及本發明效果之程度下,亦可於聚合起始劑(C)中組合使用聚合起始助劑(C-1)。
至於聚合起始助劑(C-1)列舉為胺化合物、羧酸化合物、多官能基硫醇化合物、以式(IV)表示之化合物、以式(V)或式(VI)表示之化合物等。
胺化合物列舉為三乙醇胺、甲基二乙醇胺、三異丙醇胺等之脂肪族胺化合物、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸2-乙基己酯、苯甲酸2-二甲胺基乙酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲胺基)二苯甲酮(通稱;米氏(Michler's)酮)或4,4’-雙(二乙胺基)二苯甲酮等之芳香族胺化合物。
羧酸化合物列舉為苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、甲基乙基苯基硫代乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、二甲氧基苯基硫代乙酸、氯苯基硫代乙酸、二氯苯基硫代乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘胺酸或萘氧基乙酸等之芳香族雜乙酸類。
多官能基硫醇化合物為分子內具有兩個以上硫烷基之化合物。
多官能基硫醇化合物具體而言列舉為己烷二硫醇、癸烷二硫醇、1,4-二甲基巰基苯、丁烷二硫醇雙硫代丙酸酯、丁烷二硫醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、三羥甲基丙烷叁硫代乙醇酸酯、丁烷二硫醇雙硫代丙酸酯、三羥甲基丙烷叁硫代丙酸酯、三羥甲基丙烷叁硫代甘胺酸酯、季戊四醇肆硫代丙酸酯、季戊四醇肆硫代乙醇酸酯、叁羥基乙基叁硫代丙酸酯、季戊四醇肆(3-巰基丁酸酯)或1,4-雙(3-巰基丁醯基氧基)丁烷等。
其中,具有兩個以上與脂肪族烴基之碳原子鍵結之硫烷基之化合物由於可使本發明之感光性樹脂組成物之感度變高故而更好。
以式(IV)表示之化合物為以下之化合物:
式(IV)中,以X表示之環表示可經鹵素原子取代之碳數6~12之芳香環。
Y表示氧原子、硫原子。
R21
表示碳數1~6之烷基。
R22
表示可經鹵素原子取代之碳數1~12之烷基或可經鹵素原子取代之芳基。
鹵素原子列舉為氟原子、氯原子、溴原子等。
碳數6~12之芳香環列舉為苯環、甲基苯環、二甲基苯環、乙基苯環、丙基苯環、丁基苯環、戊基苯環、己基苯環、環己基苯環、氯苯環、二氯苯環、溴苯環、二溴苯環、苯基苯環、氯苯基苯環、溴苯基苯環、萘環、氯萘環、溴萘環、菲環、屈(chrysene)環、熒蒽(Fluoranthene)環、苯并[a]芘環、苯并[e]芘環、苝環及該等之衍生物等。其中,以苯環、萘環等較佳。
可經鹵素原子取代之碳數6~12之芳香環列舉為苯環、甲基苯環、二甲基苯環、乙基苯環、丙基苯環、丁基苯環、戊基苯環、己基苯環、環己基苯環、氯苯環、二氯苯環、溴苯環、二溴苯環、苯基苯環、氯苯基苯環、溴苯基苯環、萘環、氯萘環、溴萘環等。
碳數1~6之烷基列舉為甲基、乙基、正丙基、異丙基、正丁基、1-甲基-正丙基、2-甲基-正丙基、第三丁基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、正己基、環己基等。
可經鹵素原子取代之碳數1~12之烷基列舉為甲基、乙基、正丙基、異丙基、正丁基、1-甲基-正丙基、2-甲基-正丙基、第三丁基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、正己基、環己基、1-氯-正丁基、2-氯-正丁基、3-氯-正丁基等。
可經鹵素原子取代之芳基列舉為苯基、氯苯基、二氯苯基、溴苯基、二溴苯基、氯溴苯基、聯苯基、氯聯苯基、二氯聯苯基、溴苯基、二溴苯基、萘基、氯萘基、二氯萘基、溴萘基、二溴萘基等。
以式(IV)表示之化合物具體而言列舉為下列者等:2-苯甲醯基伸甲基-3-甲基-萘并[2,1-d]噻唑啉,2-苯甲醯基伸甲基-3-甲基-萘并[1,2-d]噻唑啉,2-苯甲醯基伸甲基-3-甲基-萘并[2,3-d]噻唑啉,2-(2-萘基伸甲基)-3-甲基苯并噻唑啉,2-(1-萘基伸甲基)-3-甲基苯并噻唑啉,2-(2-萘基伸甲基)-3-甲基-5-苯基苯并噻唑啉,2-(1-萘基伸甲基)-3-甲基-5-苯基苯并噻唑啉,2-(2-萘基伸甲基)-3-甲基-5-氟苯并噻唑啉,2-(1-萘基伸甲基)-3-甲基-5-氟苯并噻唑啉,2-(2-萘基伸甲基)-3-甲基-5-氯苯并噻唑啉,2-(1-萘基伸甲基)-3-甲基-5-氯苯并噻唑啉,2-(2-萘基伸甲基)-3-甲基-5-溴苯并噻唑啉,2-(1-萘基伸甲基)-3-甲基-5-溴苯并噻唑啉,2-(4-聯苯基伸甲基)-3-甲基苯并噻唑啉,2-(4-聯苯基伸甲基)-3-甲基-5-苯基萘并噻唑啉,2-(2-萘基伸甲基)-3-甲基-萘并[2,1-d]噻唑啉,2-(2-萘基伸甲基)-3-甲基-萘并[1,2-d]噻唑啉,2-(4-聯苯基伸甲基)-3-甲基-萘并[2,1-d]噻唑啉,2-(4-聯苯基伸甲基)-3-甲基-萘并[1,2-d]噻唑啉,2-(對-氟苯甲醯基伸甲基)-3-甲基-萘并[2,1-d]噻唑啉,2-(對-氟苯甲醯基伸甲基)-3-甲基-萘并[1,2-d]噻唑啉,2-苯甲醯基伸甲基-3-甲基-萘并[2,1-d]噻唑啉,2-苯甲醯基伸甲基-3-甲基-萘并[1,2-d]噻唑啉,2-苯甲醯基伸甲基-3-甲基-萘并[2,3-d]噻唑啉,2-(2-萘基伸甲基)-3-甲基苯并噁唑啉,2-(1-萘基伸甲基)-3-甲基苯并噁唑啉,2-(2-萘基伸甲基)-3-甲基-5-苯基苯并噁唑啉,2-(1-萘基伸甲基)-3-甲基-5-苯基苯并噁唑啉,2-(2-萘基伸甲基)-3-甲基-5-氟苯并噁唑啉,2-(1-萘基伸甲基)-3-甲基-5-氟苯并噁唑啉,2-(2-萘基伸甲基)-3-甲基-5-氯苯并噁唑啉,2-(1-萘基伸甲基)-3-甲基-5-氯苯并噁唑啉,2-(2-萘基伸甲基)-3-甲基-5-溴苯并噁唑啉,2-(1-萘基伸甲基)-3-甲基-5-溴苯并噁唑啉,2-(4-聯苯基伸甲基)-3-甲基苯并噁唑啉,2-(4-聯苯基伸甲基)-3-甲基-5-苯基苯并噁唑啉,2-(2-萘基伸甲基)-3-甲基-萘并[2,1-d]噁唑啉,2-(2-萘基伸甲基)-3-甲基-萘并[1,2-d]噁唑啉,2-(4-聯苯基伸甲基)-3-甲基-萘并[2,1-d]噁唑啉,2-(4-聯苯基伸甲基)-3-甲基-萘并[1,2-d]噁唑啉,2-(對-氟苯甲醯基伸甲基)-3-甲基-萘并[2,1-d]噁唑啉、2-(對-氟苯甲醯基伸甲基)-3-甲基-萘并[1,2-d]噁唑啉。
其中,較佳者為以式(9)表示之2-(2-萘基伸甲基)-3-甲基苯并噻唑啉、以式(10)表示之2-苯甲醯基伸甲基-3-甲基-萘并[1,2-d]噻唑啉及以式(11)表示之2-(4-聯苯基伸甲基)-3-甲基-萘并[1,2-d]噻唑啉。
以式(V)及式(VI)表示之化合物為以下之化合物。
式(V)及式(VI)中,環X31
及環X32
各獨立表示碳數6~12之芳香環。Y31
及Y32
表示氧原子或硫原子。R31
及R32
表示碳數1~12之烷基或碳數6~12之芳基。
該等芳香環、烷基或芳基中所含之碳原子亦可經氧原子、氮原子、硫原子取代,該等芳香環、烷基或芳基中所含之氫原子亦可經鹵素原子取代。又,芳基中所含之氫原子亦可經羥基或烷氧基取代。
羥基取代之芳基列舉為羥基苯基、羥基萘基等。
烷氧基列舉為例如碳數1~6之烷氧基。具體而言列舉為甲氧基、乙氧基、丙氧基、丁氧基等。
烷氧基取代之芳基列舉為甲氧基苯基、乙氧基苯基、丙氧基苯基、甲氧基萘基、乙氧基萘基、丙氧基萘基等。
以式(V)或式(VI)表示之化合物具體而言列舉為下列者:二甲氧基萘、二乙氧基萘、二丙氧基萘、二異丙氧基萘、二丁氧基萘等之二烷氧基萘類,二甲氧基蒽、二乙氧基蒽、二丙氧基蒽、二異丙氧基蒽、二丁氧基蒽、二戊氧基蒽、二己氧基蒽、甲氧基乙氧基蒽、甲氧基丙氧基蒽、甲氧基異丙氧基蒽、甲氧基丁氧基蒽、乙氧基丙氧基蒽、乙氧基異丙氧基蒽、乙氧基丁氧基蒽、丙氧基異丙氧基蒽、丙氧基丁氧基蒽、異丙氧基丁氧基蒽等之二烷氧基蒽類;二甲氧基并四苯(Naphthacene)、二乙氧基并四苯、二丙氧基并四苯、二異丙氧基并四苯、二丁氧基并四苯等之二烷氧基并四苯類等。
聚合起始助劑(C-1)之含量,以相對於樹脂(A)及聚合性單體(B)之合計量之質量分率計,較好為0.01~50質量%,更好為0.1~40質量%。
尤其,使用多官能基硫醇化合物作為聚合起始助劑(C-1)時,其含量以相對於聚合起始劑(C)之質量分率計較好為0.5~20質量%,更好為1~15質量%。
又,以選自由式(V)及式(VI)所組成群組之至少一種表示之化合物之含量,相對於聚合起始助劑(C-1)之含量,較好為50~100質量%,更好為60~100質量%,又更好為65~100質量%。該等化合物之含量在該範圍內時,使用含有該等之感光性樹脂組成物形成塗膜時,由於塗膜之透明性變良好故而較佳。
聚合起始助劑(C-1)之量在前述範圍內時,有所得感光性樹脂組成物之感度變得更高,顯像性成為良好,使用該感光性樹脂組成物所形成之圖型之生產性提高之傾向。
本發明之感光性樹脂組成物含有溶劑(D)。至於溶劑(D)列舉為感光性樹脂組成物之領域中使用之各種有機溶劑。
具體例列舉為如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚及乙二醇單丁基醚之乙二醇單烷基醚類;二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚、二乙二醇二丙基醚、二乙二醇二丁基醚等之二乙二醇二烷基醚類;甲基溶纖素乙酸酯、乙基溶纖素乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙基醚乙酸酯等之乙二醇烷基醚乙酸酯類;丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯等之烷二醇烷基醚乙酸酯類;丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚等之丙二醇單烷基醚類;丙二醇二甲基醚、丙二醇二乙基醚、丙二醇乙基甲基醚、丙二醇二丙基醚、丙二醇丙基甲基醚、丙二醇乙基丙基醚等之丙二醇二烷基醚類;丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等之丙二醇烷基醚丙酸酯類;甲氧基丁基醇、乙氧基丁基醇、丙氧基丁基醇、丁氧基丁基醇等之丁二醇單烷基醚類;甲氧基丁基乙酸酯、乙氧基丁基乙酸酯、丙氧基丁基乙酸酯、丁氧基丁基乙酸酯等丁二醇單烷基醚乙酸酯類;甲氧基丁基丙酸酯、乙氧基丁基丙酸酯、丙氧基丁基丙酸酯、丁氧基丁基丙酸酯等丁二醇單烷基醚丙酸酯類;二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇甲基乙基醚等二丙二醇二烷基醚類;苯、甲苯、二甲苯、均三甲苯(mesitylene)等芳香族烴類;甲基乙基酮、丙酮、甲基戊基酮、甲基異丁基酮、環己酮等酮類;乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙三醇等醇類;乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、3-丁氧基丙酸丁酯等酯類;四氫呋喃、吡喃等環狀醚基類;γ-丁內酯等環狀酯類等。
前述溶劑(D)就塗佈性、乾燥性之觀點而言,較好包含沸點140℃以上175℃以下之溶劑。沸點175℃以下之溶劑列舉為烷二醇烷基醚乙酸酯類;甲氧基丁醇及乙氧基丁醇等醇類;環己酮等酮類;3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基乙酸乙酯、3-甲氧基乙酸丁酯、3-乙氧基乙酸丁酯等酯類。較佳者列舉為甲氧基丁醇、甲氧基丁基乙酸酯、3-乙氧基丙酸乙酯及3-甲氧基丙酸甲酯。
該等溶劑(D)可分別單獨使用,或混合兩種以上使用,且以混合兩種以上較佳。又,溶劑(D)亦可包含沸點超過175℃者。
又,溶劑(D)較好含有碳數1~6之醇者。該等醇類可由上述溶劑中適當選擇。該等醇類以沸點在175℃以下者較佳,但亦可為沸點超過175℃者。
本發明之感光性樹脂組成物中之溶劑(D)含量,以相對於感光性樹脂組成物之質量分率計,較好為60~90質量%,更好為65~85質量%。溶劑(D)之含量在該範圍內時,以後述之各種塗佈裝置塗佈時之塗佈性良好。又,包含沸點超過175℃脂溶劑時,此等溶劑以佔全部溶劑之30質量%左右以下較佳。
本發明之感光性樹脂組成物中之界面活性劑(E)並無特別限制,列舉為例如聚矽氧系界面活性劑、氟系界面活性劑、具有氟原子之聚矽氧系界面活性劑等。其中以具有氟原子之聚矽氧系界面活性劑較佳。藉由使用該等界面活性劑(E),與感光性樹脂組成物中之其他成分及其含量相結合,可防止於組成物中含有之微小氣泡發生。其結果,可有效抑止溶劑蒸發時之突沸。
至於聚矽氧系界面活性劑列舉為具有矽氧烷鍵之界面活性劑。具體而言列舉為TORAY SILICONE DC3PA、TORAY SILICONE SH7PA、TORAY SILICONE DC11PA、TORAY SILICONE SH21PA、TORAY SILICONE SH28PA、TORAY SILICONE 29SHPA、TORAY SILICONE SH30PA、聚醚改質矽氧油SH8400(商品名;東麗‧道康寧(股)製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越聚矽氧製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(GE東芝聚矽氧(股)製造)等。
氟系界面活性劑列舉為具有氟碳鏈之界面活性劑。具體而言列舉為FLUORINERT(註冊商標)FC430、FLUORINERT FC431(住友3M(股)製造)、MEGAFAC(註冊商標)F142D、MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、MEGAFAC R30(大日本油墨化學工業(股)製造)、EF Top(註冊商標)EF301、EF Top EF303、EF Top EF351、EF Top EF352(新秋田化成(股)製造)、SURFLON(註冊商標)S381、SURFLON S382、SURFLON SC101、SURFLON SC105(旭硝子(股)製造)、E5844(Daikin精密化學研究所(股)製造)、BM-1000、BM-1100(均為商品名:BM化學公司製造)等。
具有氟原子之聚矽氧系界面活性劑列舉為具有矽氧烷鍵及氟碳鏈之界面活性劑。具體而言列舉為MEGAFAC(註冊商標)R08、MEGAFAC BL20、MEGAFAC F475、MEGAFAC F477、MEGAFAC F443(大日本油墨化學工業(股)製造)等。較佳者列舉為MEGAFAC(註冊商標)F475。
界面活性劑(E)相對於除界面活性劑以外之感光性樹脂組成物100質量%,通常為0.0025~0.0250質量%,較好為0.0025~0.0200質量%,更好為0.05~0.0100質量%。藉由以該範圍含有界面活性劑,可使平坦性變好,同時如上述,可有效防止突沸。
本發明之感光性樹脂組成物亦可依據需要倂用填充劑、除樹脂(A)以外之高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑、光安定劑、抗凝集劑、鏈轉移劑等添加劑。
又,本發明之感光性樹脂組成物宜實質上不含有顏料及染料等著色劑。尤其,本發明之感光性樹脂組成物中,著色劑相對於組成物全體之含量,以質量分率計,較適宜為未達1質量%,較好小於0.5質量%。
至於填充劑列舉為玻璃、氧化矽、氧化鋁等。
至於樹脂(A)以外之高分子化合物列舉為環氧樹脂、馬來醯亞胺樹脂等硬化性樹脂或聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚丙烯酸氟烷基酯、聚酯、聚胺基甲酸酯等熱可塑性樹脂等。
至於密著促進劑較好為矽烷系化合物。具體而言列舉為乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧矽烷等。
至於抗氧化劑列舉為2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羥基-3,5-二-第三戊基苯基)乙基]-4,6-二-第三戊基苯基丙烯酸酯、6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二噁磷環庚烷(dioxaphosphepin)、3,9-雙[2-{3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯基氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一碳烷、2,2’-伸甲基雙(6-第三丁基-4-甲基酚)、4,4’-亞丁基雙(6-第三丁基-3-甲基酚)、4,4’-硫基雙(2-第三丁基-5-甲基酚)、2,2’-硫基雙(6-第三丁基-4-甲基酚)、3,3’-硫基二丙酸二月桂酯、3,3’-硫基二丙酸二肉豆蔻酯、3,3’-硫基二丙酸二硬脂酯、季戊四醇肆(3-月桂基硫基丙酸酯)、1,3,5-叁(3,5-二-第三丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮、3,3’,3’’,5,5’,5”-六-第三丁基-a,a’,a”-(三甲苯-2,4,6-三基)三-對-甲酚、季戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,6-二第三丁基-4-甲基酚等。
紫外線吸收劑列舉為2-(2-羥基-5-第三丁基苯基)-2H-苯并三唑、辛基-3-[3-第三丁基-4-羥基-5-(5-氯-2H-苯并三唑-2-基)苯基]丙酸酯、2-[4-[(2-羥基-3-十二烷基氧基丙基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-[4-[(2-羥基-3-(2’-乙基)己基)氧基]-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4-雙(2-羥基-4-丁基氧基苯基)-6-(2,4-雙-丁基氧基苯基)-1,3,5-三嗪、2-(2-羥基-4-[1-辛基氧羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三嗪、2-(2H-苯并三唑-2-基)-4,6-雙(1-甲基-1-苯基乙基)酚、2-(2H-苯并三唑-2-基)-6-(1-甲基-1-苯基乙基)-4-(1,1,3,3-四甲基丁基)酚、2-(3-第三丁基-2-羥基-5-甲基苯基)-5-氯苯并三唑或烷氧基二苯甲酮等。
光安定劑列舉為由琥珀酸與(4-羥基-2,2,6,6-四甲基哌啶-1-基)乙醇所構成之高分子、N,N’,N”,N’’’-肆(4,6-雙(丁基-(N-甲基-2,2,6,6-四甲基哌啶-4-基)胺基)三嗪-2-基)-4,7-二氮雜癸-1,10-二胺、癸二酸與雙(2,2,6,6-四甲基-1-(辛基氧基)-4-哌啶基)酯及1,1-二甲基乙基過氧化氫之反應物,雙(1,2,2,6,6-五甲基-4-哌啶基)-[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丁基丙二酸酯、2,4-雙[N-丁基-N-(1-環己基氧基-2,2,6,6-四甲基哌啶-4-基)胺基]-6-(2-羥基乙基胺)-1,3,5-三嗪、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯或甲基(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯等。
抗凝集劑列舉為聚丙烯酸鈉等。
鏈轉移劑列舉為十二烷基硫醇、2,4-二苯基-4-甲基-1-戊烯等。
本發明之感光性樹脂組成物之固形成分量以10~30重量%左右較佳,更好為12~28重量%,又更好為15~25重量%。藉由在該範圍內,即使利用各種塗佈方法,尤其是狹縫模嘴法,亦可形成不產生缺陷或霧狀斑點之均勻塗膜。
又,本發明之感光性樹脂組成物充填於光路長1cm之石英胞(cell)中,使用分光光度計,在測定波長400~700nm之條件下測定透過率時,透過率通常為70%以上,較好為80%以上。
本發明之感光性樹脂組成物作成塗膜時,塗膜之透過率以90%以上較佳,更好為95%以上。該透過率係對加熱硬化(例如,100~250℃,5分鐘至3小時)後之厚度為3μm之塗膜,使用分光光度計,在測定波長400~700nm之條件下測定時之值。據此,可提供透明性優異之塗膜。
本發明之感光性樹脂組成物可如後所述般,藉由塗佈於基材;玻璃、金屬、塑膠等基板;形成彩色濾光片、各種絕緣或導電膜、驅動電路等之該基板等之上,形成塗膜。塗膜以經乾燥及硬化者較佳。又,可使所得之塗膜圖形化成所需形狀,作為圖型使用。再者,亦可形成該等塗膜或圖型作為顯示裝置等之構成構件之一部分。
首先,將本發明之感光性樹脂組成物塗佈於基材或由以往形成之感光性樹脂組成物之固形成分所構成之層上。
塗佈方法並無特別限制,可使用例如旋轉塗佈法、狹縫與旋轉塗佈法、狹縫模具塗佈法(有時亦稱為模具塗佈法、淋幕塗佈法)、噴墨法、輥塗佈、浸漬塗佈等塗佈裝置進行。其中,就溶解性、防止乾燥、防止異物發生等而言,以利用狹縫模具塗佈法塗佈,尤其是狹縫與旋轉塗佈以及狹縫模具塗佈等較佳。
接著,較好經乾燥或預烘烤去除溶劑等揮發成分。據此,可獲得平滑之未硬化塗膜。尤其,以進行減壓乾燥較佳。此處之減壓乾燥可去除溶劑之至少一部份,只要以不妨礙後續步驟之程度去除即可,並無必要自塗膜完全去除溶劑。減壓乾燥較好在室溫(25℃)之條件下,在常壓至達到壓力10~500Pa之範圍內進行,更好為30~400Pa,又更好為50~300Pa。減壓乾燥時間並無限制,可考慮膜厚、基板之大小、感光性樹脂組成物之溶劑量等適宜設定。通常以10秒~60秒較佳。由於使用此等較嚴苛之減壓乾燥條件,因此達到最終達到壓力為止之減壓速度亦可多階段變化。例如,以自常壓至130Pa為止所需之時間為10秒左右,自130Pa至66Pa為止為10秒左右之兩階段方式控制減壓速度,可獲得更平滑之未硬化膜。
此時之塗膜膜厚並無特別限制,可依據使用之材料、用途等適宜調整,通常例示為0.1~30μm左右,較好為1~20μm左右,更好為1~6μm左右。
接著,透過用以形成目的圖型之光罩對所得未硬化塗膜照射光例如由水銀燈、發光二極體等產生之紫外線等。此時光罩之形狀並無特別限制,列舉有各種形狀。又,線寬等亦可依據光罩尺寸等適度調整。
近年之曝光機係將小於350nm之光使用截取此光波長區域之濾波器截取掉,或是將436nm附近、408nm附近、365nm附近之光以使用可濾掉此等波長區域之帶通濾波器(bandpass filter)予以選擇地取出,而可對曝光面全體均勻地照射平行光線。為了使此時之光罩與基材之位置正確對準,亦可使用光罩對準器、步進機器等。
隨後,可藉由使塗膜接觸於鹼性水溶液使特定部分例如未曝光部份溶解、顯像,獲得目標之圖型形狀。
顯像方法可為溢液法、浸漬法、噴佈法等之任一種。再者顯像時可以任意角度使基材傾斜。
顯像時使用之顯像液通常為包含鹼性化合物與界面活性劑之水溶液。
鹼性化合物為無機或有機鹼性化合物之任一種。
無機鹼性化合物列舉為氫氧化鈉、氫氧化鉀、磷酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸二氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、硼酸鈉、硼酸鉀、或氨等。
又,作為有機鹼性化合物列舉為氫氧化四甲基銨、氫氧化2-羥基乙基三甲基銨、單甲胺、二甲胺、三甲胺、單乙胺、二乙胺、三乙胺、單異丙基胺、二異丙基胺或乙醇胺等。
鹼顯像液中鹼性化合物之濃度較好為0.01~10質量%,更好為0.03~5質量%。
又,鹼性顯像液中之界面活性劑為非離子系界面活性劑或陰離子系界面活性劑,或陽離子系界面活性劑之任一種。
非離子系界面活性劑列舉為聚氧乙烯烷基醚、聚氧乙烯芳基醚、聚氧乙烯烷基芳基醚、其他之聚氧乙烯衍生物、氧乙烯/氧丙烯嵌段共聚物、山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂肪酸酯、丙三醇脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺等。
陰離子系界面活性劑列舉為月桂醇硫酸酯鈉或油醇硫酸酯納等之高級醇硫酸酯鹽類,月桂基硫酸鈉或月桂基硫酸銨等烷基硫酸鹽類,十二烷基苯磺酸鈉或十二烷基萘磺酸鈉等烷基芳基磺酸鹽類等。
陽離子系界面活性劑列舉為硬脂基胺鹽酸鹽或氯化月桂基三甲基銨等胺鹽或四級銨鹽等。
鹼顯像液中之界面活性劑之濃度較好為0.01~10質量%之範圍,更好為0.05~8質量%之範圍,又更好為0.1~5質量%。
顯像後進行水洗,另亦可依據需要進行後烘烤,後烘烤較好在150~230℃之溫度範圍進行10~180分鐘。
尤其,本發明之感光性樹脂組成物較好使用狹縫模嘴塗佈器將本發明之感光性樹脂組成物塗佈於基板上形成膜,基板上形成之膜經減壓乾燥,藉此製造塗膜。
又,較好透過光罩使所得塗膜曝光,使經曝光之塗膜顯像藉此製造圖型。
如此獲得之塗膜或圖型可使用作為例如液晶顯示裝置所使用之光隔離器、可圖型化之上塗層。又,對未硬化塗膜進行圖型化曝光時,藉由使用孔洞形成用光罩,可形成孔洞,且可用作層間絕緣膜。再者,對未硬化塗膜進行曝光時,可不使用光罩,僅藉由進行全面曝光及加熱硬化或加熱硬化,而形成透明膜。此透明膜可使用作為上塗層。又,亦可使用於觸控面板等之顯示裝置中。藉此,可以高良率製造具備有高品質塗膜或圖型之顯示裝置。
本發明之感光性樹脂組成物為用以形成各種模及圖型之材料而可較好地用於形成例如透明膜尤其是構成彩色濾光片之一部分之透明膜、圖型、光隔離器、上塗層、絕緣膜、液晶配向控制用突起、微透鏡、組合不同膜厚之著色圖型、塗層等。又,可利用於具備該等塗膜或圖型作為其構成構件之一部份之彩色濾光器、陣列基板等,進而可利用於具備有該等彩色濾光片及/或陣列基板等之顯示裝置例如液晶顯示裝置、有機EL裝置等。
依據本發明之感光性樹脂組成物,可形成起因於溶劑突沸之缺陷或霧狀斑點等之發生受到抑制、塗膜全體為均一之高品質塗膜。
又,藉由使用此等感光性樹脂組成物,可獲得高品質之顯示裝置。
實施例
以下由實施例更詳細說明本發明,但本發明並不因該等實施例而受限。又,以下實施例及比較例中,表示含量或使用量之%或份若未特別說明則為質量基準。
合成例1
使氮氣以0.02L/分鐘流入具備回流冷卻器、滴加漏斗及攪拌機之1升燒瓶內使成為氮氣氛圍,加入200質量份之3-甲氧基-1-丁醇及105質量份之乙酸3-甲氧基丁酯,邊攪拌邊加熱至70℃。
接著,將60質量份之甲基丙烯酸、240質量份之丙烯酸3,4-環氧基三環[5.2.1.02.6
]癸酯(以式(I-1)表示之化合物及以式(II-1)表示之化合物之混合物,莫耳比=50:50)溶解於140質量份之乙酸3-甲氧基丁酯中,調製溶液。
使用滴加漏斗,將所得溶解液於4小時內滴加於在70℃保溫之燒瓶內。
另一方面,使用另一滴加漏斗,於4小時內將使45質量份之聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)溶解於225質量份之乙酸3-甲氧基丁酯而成之溶液滴加於燒瓶內。
聚合起始劑之溶液滴加結束後,維持在70℃4小時,隨後冷卻至室溫,獲得固形成分32.3質量%、酸價35.6mg-KOH/g之共聚物(樹脂Aa)之樹脂溶液。所得樹脂Aa之重量平均分子量Mw為9.1x103
,分散度為2.02。
合成例2
使氮氣以0.02L/分鐘流入具備回流冷卻器、滴加漏斗及攪拌機之1升燒瓶內使成為氮氣氛圍,加入140質量份之二乙二醇乙基甲基醚,邊攪拌邊加熱至70℃。
接著,將40質量份之甲基丙烯酸、360質量份之丙烯酸3,4-環氧基三環[5.2.1.02.6
]癸酯(以式(I-1)表示之化合物及以式(II-1)表示之化合物之混合物,莫耳比=50:50)溶解於190質量份之二乙二醇乙基甲基醚中,調製溶液。
使用滴加漏斗,將所得溶解液於4小時內滴加於在70℃保溫之燒瓶內。
另一方面,使用另一滴加漏斗,於5小時內將使30質量份之聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)溶解於240質量份之二乙二醇乙基甲基醚而成之溶液滴加於燒瓶內。
聚合起始劑之溶液滴加結束後,維持在70℃4小時,隨後冷卻至室溫,獲得固形成分42.6質量%、酸價60mg-KOH/g之共聚物(樹脂Ab)之溶液。所得樹脂Ab之重量平均分子量Mw為8.0x103
,分散度為1.91。
前述黏合劑聚合物之重量平均分子量(Mw)及數平均分子量(Mn)之測定係使用GPC法,於下列條件進行。
裝置;K2479(島津製作所(股)製造)
管柱;島津Shim-pack GPC-80M
管柱溫度;40℃
溶劑;THF(四氫呋喃)
流速;1.0mL/min
檢出器;RI
於上述獲得之聚苯乙烯換算之重量平均分子量及數平均分子量之比作為分散度(Mw/Mn)。
實施例1~8、比較例1~3
以表1之組成混合各成分,獲得感光性樹脂組成物。又,表1中
聚合性單體(B):二季戊四醇六丙烯酸酯(KAYARAD DPHA;日本化藥(股)製造)
聚合起始劑(C);2-甲基-1-(4-甲基硫烷基苯基)-2-嗎啉基丙-1-酮(Irgacure 907;汽巴特用化學品公司製造)
溶劑(Da);3-甲氧基-1-丁醇(沸點161℃)
溶劑(Db);3-乙氧基丙酸乙酯(沸點170℃)
溶劑(Dc);乙酸3-甲氧基丁酯(沸點171℃)
溶劑(Dd);二乙二醇乙基甲基醚(沸點176℃)
溶劑(De);丙二醇單甲基醚乙酸酯(沸點146℃)
溶劑(Df);苄基醇(沸點205℃)
溶劑(Dg);乙二醇單丁基醚乙酸酯(沸點192℃)
界面活性劑(E);聚醚改質矽氧油(東麗‧道康寧(股)製造,SH8400)
溶劑(D)係使組成物之固形成分成為表1之「固成分量(%)」般予以混合,溶劑(D)中之溶劑成分值係表示溶劑(D)中之質量比。界面活性劑(E)之含量表示相對於除界面活性劑以外之感光性樹脂組成物100質量%之質量比。
<突沸及霧狀斑點之評價>
使用狹縫模嘴塗佈器(卓Die-100,伊藤忠產機股份有限公司製造),以使硬化後之膜厚成為3.0μm之條件將所調製之組成物溶液塗佈於邊長15cm之ITO成膜玻璃基板上。隨後,以減壓乾燥機(VCD Microtech(股)製造)將減壓度減壓至0.5torr並乾燥,進而,在加熱板上,於90℃下預烘乾2分鐘,形成塗膜A。
使所得塗膜A冷卻,以Na燈照射其表面,以目視確認塗膜表面。
可清楚確認出突沸引起之缺陷時判定為×,稍可確認時判定為△,幾乎無法確認時判定為○。
可清楚確認出霧狀斑點時判定為×,稍可確認時判定為△,幾乎無法確認時判定為○。
<均勻度之評價>
對所得塗膜A,測定與端部距離12.5mm以內以12.5mm間隔並列於矩陣上之測定點之膜厚。求得最大膜厚、最小膜厚、平均膜厚,以式(1)進行評價。
均勻度(%)=(最大膜厚×最小膜厚)/(2×平均膜厚)×100(1)
均勻度小於3%時判定為○,3~5%時判定為△,5%以上時判定為×。
<減壓乾燥時間之評價>
使用狹縫模嘴塗佈器(卓Die-100,伊藤忠產機股份有限公司製造),以使硬化後之膜厚成為3.0μm之條件將所調製之組成物溶液塗佈於邊長15cm之ITO成膜玻璃基板上。隨後,以減壓乾燥機(VCD Microtech(股)製造),旋轉泵浦轉速為1800rpm,加壓泵浦(Booster Pump)轉數為3600rpm,常溫25℃之條件下測定使減壓度達到66Pa之時間(以下稱為VCD時間)。
VCD時間較短者較有利。
本發明之感光性樹脂組成物可對大面積之全面進行均勻塗佈,同時可抑制因溶劑之突沸引起之缺陷或霧狀斑點等。又,可形成顯示優異解像度、高透過率之圖型。而且,可適當地使用於形成上塗層、光隔離器、絕緣膜、控制液晶配向用突起、配合著色圖型之膜厚之塗層等之於顯示裝置中使用之塗膜或圖型。
Claims (8)
- 一種感光性樹脂組成物,其為包含樹脂(A)、聚合性單體(B)、聚合起始劑(C)、溶劑(D)及界面活性劑(E)之感光性樹脂組成物,樹脂(A)係包含由樹脂(A2-1)及樹脂(A2-3)所構成群組選出的至少一種樹脂,其中,該樹脂(A2-1)係由不飽和羧酸及不飽和羧酸酐所構成群組選出的至少一種(A-a)、可與前述(A-a)共聚合之單體(A-b)(但排除前述(A-a))以及具有含有碳數2~4之環狀醚鍵之基之單體(A-c)所成的共聚物,該樹脂(A2-3)係由不飽和羧酸及不飽和羧酸酐所構成群組選出的至少一種(A-a)以及具有含有碳數2~4之環狀醚鍵之基之單體(A-c)所成的共聚物,該(A-c)係包含於脂肪族單環式化合物的環上或脂肪族多環式化合物的環上具有脂環式環氧基之聚合性化合物的單體,溶劑(D)係包含兩種以上沸點為175℃以下之溶劑之溶劑,界面活性劑(E)之含量係相對於界面活性劑除外之感光性樹脂組成物100重量%而言為0.0025~0.0250重量%,且該感光性樹脂組成物之固形成分量為10~30重量%。
- 如申請專利範圍第1項之感光性樹脂組成物,其 中溶劑(D)為包含兩種以上沸點為140℃以上175℃以下之溶劑的溶劑。
- 如申請專利範圍第1或2項之感光性樹脂組成物,其中溶劑(D)係包含碳數1~6之醇的溶劑。
- 如申請專利範圍第3項之感光性樹脂組成物,其中溶劑(D)係包含3-甲氧基丁醇之溶劑。
- 如申請專利範圍第1或2項之感光性樹脂組成物,其中界面活性劑(E)係選自由聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑所組成群組之至少一種。
- 一種塗膜,其特徵為使用申請專利範圍第1至5項中任一項之感光性樹脂組成物所形成。
- 一種圖型,其特徵為使用申請專利範圍第1至5項中任一項之感光性樹脂組成物所形成。
- 一種顯示裝置,其特徵為包含申請專利範圍第6項之塗膜及/或申請專利範圍第7項之圖型。
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