JPH04352101A - Radiation sensitive resin composition for microlens - Google Patents
Radiation sensitive resin composition for microlensInfo
- Publication number
- JPH04352101A JPH04352101A JP3153729A JP15372991A JPH04352101A JP H04352101 A JPH04352101 A JP H04352101A JP 3153729 A JP3153729 A JP 3153729A JP 15372991 A JP15372991 A JP 15372991A JP H04352101 A JPH04352101 A JP H04352101A
- Authority
- JP
- Japan
- Prior art keywords
- compd
- acid
- resin
- microlenses
- epoxy
- 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.)
- Granted
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 24
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 11
- 230000002285 radioactive effect Effects 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 27
- 238000010438 heat treatment Methods 0.000 abstract description 23
- 229920003986 novolac Polymers 0.000 abstract description 14
- 239000004593 Epoxy Substances 0.000 abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 21
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 20
- -1 m-cresol Chemical compound 0.000 description 19
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000003822 epoxy resin Substances 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 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 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920003319 Araldite® Polymers 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 5
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KIJJAQMJSXOBIE-UHFFFAOYSA-N (2-methylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC1CCCCC1OC(=O)C(C)=C KIJJAQMJSXOBIE-UHFFFAOYSA-N 0.000 description 2
- SSLASPHAKUVIRG-UHFFFAOYSA-N (2-methylcyclohexyl) prop-2-enoate Chemical compound CC1CCCCC1OC(=O)C=C SSLASPHAKUVIRG-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- QSKPIOLLBIHNAC-UHFFFAOYSA-N 2-chloro-acetaldehyde Chemical compound ClCC=O QSKPIOLLBIHNAC-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- XQDNFAMOIPNVES-UHFFFAOYSA-N 3,5-Dimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1 XQDNFAMOIPNVES-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- FKIRSCKRJJUCNI-UHFFFAOYSA-N ethyl 7-bromo-1h-indole-2-carboxylate Chemical compound C1=CC(Br)=C2NC(C(=O)OCC)=CC2=C1 FKIRSCKRJJUCNI-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
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- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229940074369 monoethyl fumarate Drugs 0.000 description 1
- NZGGUIFHFVGRKD-UHFFFAOYSA-N n,n,2-tribromo-3,4-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CC1=C(Br)C(N(Br)Br)=CC=C1CC1CO1 NZGGUIFHFVGRKD-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はマイクロレンズ用感放射
線性樹脂組成物に関する。更に詳しくは、微小な光学レ
ンズ体およびレンズ体が規則的に配列してなるレンズア
レイ体などに使用し得るマイクロレンズ用感放射線性樹
脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition for microlenses. More specifically, the present invention relates to a radiation-sensitive resin composition for microlenses that can be used for microlenses such as minute optical lens bodies and lens array bodies in which lens bodies are regularly arranged.
【０００２】0002
【従来の技術】２０〜２００μｍ程度のレンズ径を有す
るマイクロレンズ、あるいはそれらのマイクロレンズを
規則的に配列して構成したマイクロレンズアレイは、フ
ァクシミリや電子複写機等の結像光学系に、あるいは光
ファイバコネクタの光学系等に応用されている。[Prior Art] Microlenses having a lens diameter of approximately 20 to 200 μm, or microlens arrays constructed by regularly arranging these microlenses, are used in imaging optical systems of facsimile machines, electronic copying machines, etc. It is applied to optical systems of optical fiber connectors, etc.
【０００３】前記レンズ径を有するマイクロレンズ（マ
イクロレンズアレイ）で実用されているものとして、イ
オン交換法により作製される分布屈折率型平板マイクロ
レンズおよび感光性ガラスを用いて作製される凸型マイ
クロレンズが挙げられる。[0003] Microlenses (microlens arrays) having the above-mentioned lens diameters that are in practical use include distributed index flat plate microlenses produced by an ion exchange method and convex microlenses produced using photosensitive glass. Examples include lenses.
【０００４】しかし、現在実用化されているマイクロレ
ンズは、いずれもその製造方法が複雑であり、従って製
造コストが高く、また、製造方法に由来する制約からレ
ンズの製造段階での他の部分と一体化させることができ
ない等の問題がある。さらにイオン交換法による分布屈
折率型平板マイクロレンズは、レンズ形成後に表面研磨
を行なう必要があり、また感光性ガラスを用いた凸型マ
イクロレンズは決められた形状にしか成形できないとい
う問題点を有している。そこで近年、感光性樹脂組成物
を用いてレジストパターンを形成した後、加熱処理する
ことによってレジストパターンをメルトフローさせ、マ
イクロレンズを形成する手法が試みられている。[0004] However, all of the microlenses that are currently in practical use have complicated manufacturing methods, resulting in high manufacturing costs.Also, due to constraints arising from the manufacturing method, it is difficult to integrate them with other parts at the lens manufacturing stage. There are problems such as not being able to integrate them. Furthermore, distributed index flat microlenses made using the ion exchange method require surface polishing after lens formation, and convex microlenses made from photosensitive glass have the problem that they can only be molded into a predetermined shape. are doing. Therefore, in recent years, a method has been attempted in which a resist pattern is formed using a photosensitive resin composition and then heated to cause the resist pattern to melt flow, thereby forming a microlens.
【０００５】しかしながら、このようにして得られるマ
イクロレンズの形状はレジストパターンの加熱処理の際
の条件に依存しており、任意の形状のマイクロレンズの
形成が困難であり、また形成後のマイクロレンズの耐熱
変形性、透明性等にも解決すべき問題が残されている。However, the shape of the microlens obtained in this way depends on the conditions during the heat treatment of the resist pattern, and it is difficult to form a microlens with an arbitrary shape. There are still problems to be solved regarding heat deformation resistance, transparency, etc.
【０００６】[0006]
【発明が解決すべき課題】本発明の目的は、マイクロレ
ンズ用感放射線性樹脂組成物を提供することにある。本
発明の他の目的は、任意の形状のマイクロレンズを作製
する際の加熱処理の条件依存性が小さく、しかも耐熱変
形性および透明性に優れたレンズを与えるマイクロレン
ズ用樹脂組成物を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a radiation-sensitive resin composition for microlenses. Another object of the present invention is to provide a resin composition for microlenses that is less dependent on heat treatment conditions when producing microlenses of arbitrary shapes and provides lenses with excellent heat deformation resistance and transparency. There is a particular thing.
【０００７】本発明のさらに他の目的および利点は以下
の説明から明らかとなろう。Further objects and advantages of the invention will become apparent from the following description.
【０００８】[0008]
【課題を解決するための手段】本発明によれば、本発明
の上記目的および利点は、（Ａ）アルカリ可溶性樹脂、
（Ｂ）感放射線性酸生成化合物（以下、「酸生成化合物
」という）および（Ｃ）エポキシ基を分子内に少くとも
２個有する化合物（以下、「エポキシ化合物」という）
、を含有することを特徴とするマイクロレンズ用感放射
線性樹脂組成物によって達成される。According to the present invention, the above objects and advantages of the present invention are achieved by: (A) an alkali-soluble resin;
(B) a radiation-sensitive acid-generating compound (hereinafter referred to as "acid-generating compound") and (C) a compound having at least two epoxy groups in the molecule (hereinafter referred to as "epoxy compound")
This is achieved by a radiation-sensitive resin composition for microlenses, which is characterized by containing the following.
【０００９】以下、本発明の構成成分について記述する
。
（Ａ）アルカリ可溶性樹脂
本発明に用いられるアルカリ可溶性樹脂は、アルカリ水
溶液に可溶な樹脂をいい、例えばノボラック樹脂および
α，β−不飽和カルボン酸の共重合体（以下、「共重合
体Ｉ」という）を挙げることができる。The constituent components of the present invention will be described below. (A) Alkali-soluble resin The alkali-soluble resin used in the present invention refers to a resin soluble in an alkaline aqueous solution, such as a copolymer of a novolac resin and an α,β-unsaturated carboxylic acid (hereinafter referred to as “copolymer I ).
【００１０】ノボラック樹脂は、フェノール類を、酸性
触媒の存在下、アルデヒド類と縮合させることにより得
られる。このフェノール類としては、例えばフェノール
、ｍ−クレゾール、ｏ−クレゾール等のクレゾール類；
２，５−キシレノール、３，５−キシレノール、３，４
−キシレノール、２，３−キシレノール等のキシレノー
ル類；ｍ−エチルフェノール、ｐ−エチルフェノール、
ｏ−エチルフェノール、ｐ−ｔ−ブチルフェノール等の
アルキルフェノール類；ｐ−メトキシフェノール、ｍ−
メトキシフェノール、３，５−ジメトキシフェノール、
２−メトキシ−４−メチルフェノール、ｍ−エトキシフ
ェノール、ｐ−エトキシフェノール、ｍ−プロポキシフ
ェノール、ｐ−プロポキシフェノール、ｍ−ブトキシフ
ェノール、ｐ−ｔ−ブトキシフェノール等のアルコキシ
フェノール類；２−メチル−４−イソプロピルフェノー
ル等のビスアルキルフェノール類；ｍ−クロロフェノー
ル、ｐ−クロロフェノール、ｏ−クロロフェノール、ジ
ヒドロキシビフェニル、ビスフェノールＡ、フェニルフ
ェノール、レゾルシノール、ナフトール等のヒドロキシ
芳香族化合物を使用することができる。Novolac resins are obtained by condensing phenols with aldehydes in the presence of an acidic catalyst. Examples of the phenols include phenol, cresols such as m-cresol, and o-cresol;
2,5-xylenol, 3,5-xylenol, 3,4
-Xylenol such as xylenol, 2,3-xylenol; m-ethylphenol, p-ethylphenol,
Alkylphenols such as o-ethylphenol and pt-butylphenol; p-methoxyphenol, m-
Methoxyphenol, 3,5-dimethoxyphenol,
Alkoxyphenols such as 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, pt-butoxyphenol; 2-methyl- Bisalkylphenols such as 4-isopropylphenol; hydroxyaromatic compounds such as m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used.
【００１１】またアルデヒド類としては、例えばホルム
アルデヒド、パラホルムアルデヒド、アセトアルデヒド
、プロピルアルデヒド、ベンズアルデヒド、フェニルア
セトアルデヒド、α−フェニルプロピルアルデヒド、β
−フェニルプロピルアルデヒド、ｏ−ヒドロキシベンズ
アルデヒド、ｍ−ヒドロキシベンズアルデヒド、ｐ−ヒ
ドロキシベンズアルデヒド、ｏ−クロロベンズアルデヒ
ド、ｍ−クロロベンズアルデヒド、ｐ−クロロベンズア
ルデヒド、ｏ−ニトロベンズアルデヒド、ｍ−ニトロベ
ンズアルデヒド、ｐ−ニトロベンズアルデヒド、ｏ−メ
チルベンズアルデヒド、ｍ−メチルベンズアルデヒド、
ｐ−メチルベンズアルデヒド、ｐ−エチルベンズアルデ
ヒド、ｐ−ｎ−ブチルベンズアルデヒド、フルフラール
、クロロアセトアルデヒドおよびこれらのアセタール体
、例えばクロロアセトアルデヒド、ジエチルアセタール
等を使用することができる。これらの中で、ホルムアル
デヒドを使用するのが好ましい。Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, and β-phenylpropylaldehyde.
- phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals thereof, such as chloroacetaldehyde, diethyl acetal, and the like can be used. Among these, it is preferred to use formaldehyde.
【００１２】アルデヒド類は、フェノール類１モルに対
して、通常、０．７〜３モル、好ましくは１．１〜２モ
ルの割合で使用される。The aldehyde is generally used in a proportion of 0.7 to 3 mol, preferably 1.1 to 2 mol, per 1 mol of the phenol.
【００１３】酸性触媒としては塩酸、硫酸、ギ酸、酢酸
およびシュウ酸等を使用することができる。As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, etc. can be used.
【００１４】これらの酸性触媒の使用量は、フェノール
類およびアルデヒド類（以下、「反応原料」という）の
合計量１モル当たり１×１０−４〜５×１０−１が好ま
しい。The amount of these acidic catalysts used is preferably 1 x 10-4 to 5 x 10-1 per mole of the total amount of phenols and aldehydes (hereinafter referred to as "reaction raw materials").
【００１５】縮合反応においては、通常、反応媒質とし
て水を用いるが、縮合反応に使用するフェノール類がア
ルデヒド類の水溶液に溶解せず、反応初期から不均一系
になる場合には、反応媒質として親水性溶媒を使用する
ことができる。In the condensation reaction, water is usually used as the reaction medium, but if the phenol used in the condensation reaction does not dissolve in the aqueous solution of aldehydes and the reaction becomes a heterogeneous system from the initial stage, water may be used as the reaction medium. Hydrophilic solvents can be used.
【００１６】かかる溶媒としては、例えばメタノール、
エタノール、プロパノール、ブタノール等のアルコール
類；アセトン、メチルエチルケトン、メチルイソブチル
ケトン等のケトン類；テトラヒドロフラン、ジオキサン
等の環状エーテル類を例示することができる。Examples of such solvents include methanol,
Examples include alcohols such as ethanol, propanol and butanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and cyclic ethers such as tetrahydrofuran and dioxane.
【００１７】これらの反応媒質の使用量は、反応原料１
００重量部あたり５０〜１，０００重量部が一般的であ
る。縮合反応時の反応温度は、反応原料の反応性に応じ
て適宜調整することができるが、通常、１０〜１５０℃
であり、好ましくは７０〜１３０℃である。The amounts of these reaction media used are as follows:
50 to 1,000 parts by weight per 00 parts by weight is common. The reaction temperature during the condensation reaction can be adjusted as appropriate depending on the reactivity of the reaction raw materials, but is usually 10 to 150°C.
and preferably 70 to 130°C.
【００１８】共重合体Ｉはα，β−不飽和カルボン酸と
他のラジカル重合性化合物とを溶媒中でラジカル重合す
ることにより得ることができる。このα，β−不飽和カ
ルボン酸としては、例えばアクリル酸、メタクリル酸、
クロトン酸等のモノカルボン酸；マレイン酸、フマル酸
、シトラコン酸、メサコン酸、イタコン酸等のジカルボ
ン酸等を挙げることができる。Copolymer I can be obtained by radical polymerizing an α,β-unsaturated carboxylic acid and another radically polymerizable compound in a solvent. Examples of the α,β-unsaturated carboxylic acid include acrylic acid, methacrylic acid,
Examples include monocarboxylic acids such as crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid.
【００１９】また他のラジカル重合性化合物としては、
例えば酸無水物、例えば無水マレイン酸、無水イタコン
酸等；ジカルボン酸モノエステル、例えばマレイン酸モ
ノエチル、フマル酸モノエチル、イタコン酸モノエチル
等；共役ジオレフィン、例えば１，３−ブタジエン、イ
ソプレン、クロロプレン、ジメチル−１，３−ブタジエ
ン等；モノオレフィン系不飽和化合物、例えばメチルメ
タクリレート、エチルメタクリレート、ｎ−ブチルメタ
クリレート、ｓｅｃ−ブチルメタクリレート、ｔ−ブチ
ルメタクリレートの如きメタクリル酸アルキルエステル
、メチルアクリレート、イソプロピルアクリレートの如
きアクリル酸アルキルエステル、シクロヘキシルメタク
リレート、２−メチルシクロヘキシルメタクリレートの
如きメタクリル酸環状アルキルエステル、シクロヘキシ
ルアクリレート、２−メチルシクロヘキシルアクリレー
トの如きアクリル酸環状アルキルエステル、フェニルメ
タクリレート、ベンジルメタクリレートの如きメタクリ
ル酸アリールエステル、フェニルアクリレート、ベンジ
ルアクリレートの如きアクリル酸アリールエステル、ス
チレン、α−メチルスチレン、ｏ−メチルスチレン、ｍ
−メチルスチレン、ｐ−メチルスチレン、ｐ−メトキシ
スチレン、アクリロニトリル、メタクリロニトリル、塩
化ビニル、塩化ビニリデン、アクリルアミド、メタクリ
ルアミド、酢酸ビニル等を用いることができる。[0019] Other radically polymerizable compounds include:
For example, acid anhydrides, such as maleic anhydride, itaconic anhydride, etc.; dicarboxylic acid monoesters, such as monoethyl maleate, monoethyl fumarate, monoethyl itaconate, etc.; conjugated diolefins, such as 1,3-butadiene, isoprene, chloroprene, dimethyl -1,3-butadiene, etc.; monoolefinically unsaturated compounds, such as methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, methyl acrylate, isopropyl acrylate, etc. Acrylic acid alkyl esters, cyclohexyl methacrylate, methacrylic acid cyclic alkyl esters such as 2-methylcyclohexyl methacrylate, acrylic acid cyclic alkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, methacrylic acid aryl esters such as phenyl methacrylate, benzyl methacrylate, phenyl acrylate, acrylic acid aryl ester such as benzyl acrylate, styrene, α-methylstyrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. can be used.
【００２０】共重合体Ｉのα，β−不飽和カルボン酸の
共重合割合は、好ましくは５〜４０重量％、特に好まし
くは１５〜３０重量％である。５重量％未満であると、
得られる共重合体がアルカリ水溶液に溶解しにくくなる
ので現像残りを生じ易く十分なるレジストパターンを作
り難い。逆に４０重量％を超えると、得られる共重合体
のアルカリ水溶液に体する溶解性が大きくなりすぎて未
露光部の溶解、即ち膜現像を防ぐことが難しくなる。ま
た、他のラジカル重合性化合物としては、得られる共重
合体の性質等から共役ジオレフィンまたはモノオレフィ
ン系不飽和化合物が好ましい。The copolymerization ratio of α,β-unsaturated carboxylic acid in copolymer I is preferably 5 to 40% by weight, particularly preferably 15 to 30% by weight. If it is less than 5% by weight,
Since the obtained copolymer becomes difficult to dissolve in an aqueous alkaline solution, it is easy to cause residual development and it is difficult to form a sufficient resist pattern. On the other hand, if it exceeds 40% by weight, the solubility of the resulting copolymer in an alkaline aqueous solution becomes too high, making it difficult to prevent unexposed areas from dissolving, that is, film development. Further, as the other radically polymerizable compound, a conjugated diolefin or a monoolefin-based unsaturated compound is preferable in view of the properties of the resulting copolymer.
【００２１】この共役ジオレフィンを用いると、ゴム特
有の柔軟性を共重合体に与えることができるので、共重
合体に柔軟性が生じ、共重合体の割れがなくなり、製品
の歩留りを著しく向上させることができる。また、基板
に対する共重合体の密着力が高まる。さらに、共役ジオ
レフィンの共重合量を増やすと得られた共重合体の溶融
温度は低温側に移行するようになる。[0021] By using this conjugated diolefin, the flexibility peculiar to rubber can be imparted to the copolymer, resulting in flexibility in the copolymer, eliminating cracks in the copolymer, and significantly improving the yield of the product. can be done. Furthermore, the adhesion of the copolymer to the substrate is increased. Furthermore, when the amount of copolymerized conjugated diolefin is increased, the melting temperature of the resulting copolymer shifts to a lower temperature side.
【００２２】また、モノオレフィン系不飽和化合物を共
重合体中に含有させることによって、共重合体の機械的
特性を適度にコントロールし、前述したアルカリ水溶液
に可溶な成分との関係によりアルカリ水溶液に体する溶
解性を微妙に調整することができる。[0022] Furthermore, by incorporating a monoolefinically unsaturated compound into the copolymer, the mechanical properties of the copolymer can be moderately controlled, and due to the relationship with the components soluble in the alkali aqueous solution mentioned above, it is possible to It is possible to finely adjust the solubility in the body.
【００２３】モノオレフィン系不飽和化合物としては、
例えばメチルメタクリレート、エチルメタクリレート、
ｎ−ブチルメタクリレート、ｓｅｃ−ブチルメタクリレ
ート、ｔ−ブチルメタクリレート等のメタクリル酸アル
キルエステル；メチルアクリレート、イソプロピルアク
リレート等のアクリル酸アルキルエステル；シクロヘキ
シルメタクリレート、２−メチルシクロヘキシルメタク
リレート等のメタクリル酸環状アルキルエステル；シク
ロヘキシルアクリレート、２−メチルシクロヘキシルア
クリレート等のアクリル酸環状アルキルエステル；フェ
ニルメタクリレート、ベンジルメタクリレート等のメタ
クリル酸アリールエステル；フェニルアクリレート、ベ
ンジルアクリレート等のアクリル酸アリールエステル；
マレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジ
エチル等のジカルボン酸のジエステル類；２−ヒドロキ
シエチルメタクリレート、２−ヒドロキシプロピルメタ
クリレート等のヒドロキシアルキルエステル類；スチレ
ン、α−メチルスチレン、ｏ−メチルスチレン、ｍ−メ
チルスチレン、ｐ−メチルスチレン、ビニルトルエン、
ｐ−メトキシスチレン、アクリロニトリル、メタクリロ
ニトリル、塩化ビニル、塩化ビニリデン、アクリルアミ
ド、メタクリルアミド、酢酸ビニル等を用いることがで
きる。As monoolefinically unsaturated compounds,
For example, methyl methacrylate, ethyl methacrylate,
Methacrylic acid alkyl esters such as n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cyclic alkyl esters such as cyclohexyl methacrylate and 2-methylcyclohexyl methacrylate; cyclohexyl Acrylic acid cyclic alkyl esters such as acrylate and 2-methylcyclohexyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;
Diesters of dicarboxylic acids such as diethyl maleate, diethyl fumarate, and diethyl itaconate; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, o-methylstyrene, m -methylstyrene, p-methylstyrene, vinyltoluene,
p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. can be used.
【００２４】これらの化合物は一種または二種以上を混
合して使用することができる。モノオレフィン系不飽和
化合物が諸特性に与える影響を考慮するとその好ましい
共重合量は、２５〜９０重量％、特に好ましくは３０〜
８０重量％である。モノオレフィン系不飽和化合物の含
有量が２５重量％未満では、樹脂中の他の成分、即ち共
役ジオレフィン系化合物やアルカリ水溶液に可溶な成分
であるα，β−不飽和カルボン酸の含量が増加するので
、樹脂の機械的物性やアルカリ現像性のコントロールが
難しくなり、他方９０重量％を超えると、相対的にアル
カリ水溶液に対する樹脂の溶解度が減ずるようになるの
で好ましくない。These compounds can be used alone or in combination of two or more. Considering the influence of the monoolefinically unsaturated compound on various properties, the preferred copolymerization amount is 25 to 90% by weight, particularly preferably 30 to 90% by weight.
It is 80% by weight. If the content of the monoolefinic unsaturated compound is less than 25% by weight, the content of other components in the resin, that is, the content of the conjugated diolefinic compound and the α,β-unsaturated carboxylic acid, which is a component soluble in an aqueous alkali solution, will decrease. If the amount increases, it becomes difficult to control the mechanical properties and alkali developability of the resin, while if it exceeds 90% by weight, the solubility of the resin in an aqueous alkaline solution will relatively decrease, which is not preferable.
【００２５】共重合体Ｉを製造する際に用いられる溶媒
としては、例えばメタノール、エタノール等のアルコー
ル類；テトラヒドロフラン等のエーテル類；エチレング
リコールモノメチルエーテル等のグリコールエーテル類
；メチルセロソルブアセテート等のセロソルブエステル
類；その他に芳香族炭化水素類、ケトン類、エステル類
等が挙げられる。Examples of solvents used in producing copolymer I include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether; and cellosolve esters such as methyl cellosolve acetate. Other examples include aromatic hydrocarbons, ketones, and esters.
【００２６】ラジカル重合における重合触媒としては通
常のラジカル重合開始剤が使用でき、例えば２，２′−
アゾビスイソブチロニトリル、２，２′−アゾビス−（
２，４−ジメチルバレロニトリル）、２，２′−アゾビ
ス−（４−メトキシ−２，４−ジメチルバレロニトリル
）等のアゾ化合物；ベンゾイルペルオキシド、ラウロイ
ルペルオキシド、ｔ−ブチルペルオキシピバレート、１
，１−ビス−（ｔ−ブチルペルオキシ）シクロヘキサン
等の有機過酸化物および過酸化水素等を挙げることがで
きる。過酸化物をラジカル重合開始剤に使用する場合、
還元剤を組み合せてレドックス型の開始剤としてもよい
。[0026] As a polymerization catalyst in radical polymerization, a usual radical polymerization initiator can be used, such as 2,2'-
Azobisisobutyronitrile, 2,2'-azobis-(
Azo compounds such as 2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, 1
, 1-bis-(t-butylperoxy)cyclohexane, and hydrogen peroxide. When using peroxide as a radical polymerization initiator,
It may be used in combination with a reducing agent to form a redox type initiator.
【００２７】以上のアルカリ可溶性樹脂の分子量は、本
発明の組成物の溶液を均一に塗布することが可能である
限り特に限定されるものではない。なお、前述のアルカ
リ可溶性樹脂においては、マイクロレンズを作製する際
の加熱処理時の重要性から共重合体Ｉが特に好ましい。The molecular weight of the above alkali-soluble resin is not particularly limited as long as it is possible to uniformly apply the solution of the composition of the present invention. In addition, among the above-mentioned alkali-soluble resins, copolymer I is particularly preferred because of its importance during heat treatment when producing microlenses.
【００２８】（Ｂ）酸生成化合物
酸生成化合物は放射線の照射によってカルボン酸を生成
する化合物であり、例えば１，２−ベンゾキノンジアジ
ドスルホン酸エステル、１，２−ナフトキノンジアジド
スルホン酸エステル、１，２−ベンゾキノンジアジドス
ルホン酸アミド、１，２−ナフトキノンジアジドスルホ
ン酸アミド等を挙げることができる。具体的にはＪ．Ｋ
ｏｓａｒ著“Ｌｉｇｈｔ−Ｓｅｎｓｉｔｉｖｅ Ｓｙ
ｓｔｅｍｓ”３３９〜３５２、（１９６５）、Ｊｏｈｎ
Ｗｉｌｅｙ ＆ Ｓｏｎｓ社（Ｎｅｗ Ｙｏ
ｒｋ）やＷ．Ｓ．Ｄｅ Ｆｏｒｅｓｔ著“Ｐｈｏｔｏ
ｒｅｓｉｓｔ”５０、（１９７５）、Ｍｃ Ｇｒａｗ
−Ｈｉｌｌ、Ｉｎｃ．（Ｎｅｗ Ｙｏｒｋ）に記載さ
れている１，２−キノンジアジド化合物を挙げることが
できる。(B) Acid-generating compound An acid-generating compound is a compound that generates a carboxylic acid upon irradiation with radiation, such as 1,2-benzoquinonediazide sulfonic acid ester, 1,2-naphthoquinonediazide sulfonic acid ester, and 1,2-benzoquinonediazide sulfonic acid ester. -benzoquinonediazide sulfonamide, 1,2-naphthoquinonediazide sulfonamide, and the like. Specifically, J. K
“Light-Sensitive Sy” by osar
stems” 339-352, (1965), John
Wiley & Sons (New Yo
rk) and W. S. “Photo” by De Forest
resist”50, (1975), Mc Graw
-Hill, Inc. (New York).
【００２９】これらの中で、放射線を照射した後に４０
０〜８００ｎｍの可視光線領域の吸収ができるだけ小さ
くなる化合物、例えば２，３，４−トリヒドロキシベン
ゾフェノン、２，３，４，４′−テトラヒドロキシベン
ゾフェノン、３′−メトキシ−２，３，４，４′−テト
ラヒドロキシベンゾフェノン、２，２′，５，５′−テ
トラメチル−２″，４，４′−トリヒドロキシトリフェ
ニルメタン、４，４′−［１−［４−（１−（４−ヒド
ロキシフェニル）−１−メチルエチル）フェニル］エチ
リデン］ジフェノールおよび２，４，４−トリメチル−
２′，４′，７−トリヒドロキシ−２−フェニルフラバ
ンの１，２−ベンゾキノンジアジド−４−スルホン酸エ
ステル、１，２−ナフトキノンジアジド−４−スルホン
酸エステル、１，２−ナフトキノンジアジド−５−スル
ホン酸エステル等を好ましいものとして挙げることがで
きる。Among these, after irradiation with radiation, 40
Compounds that minimize absorption in the visible light range from 0 to 800 nm, such as 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4, 4'-tetrahydroxybenzophenone, 2,2',5,5'-tetramethyl-2'',4,4'-trihydroxytriphenylmethane, 4,4'-[1-[4-(1-(4 -hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]diphenol and 2,4,4-trimethyl-
1,2-benzoquinonediazide-4-sulfonic acid ester of 2',4',7-trihydroxy-2-phenylflavan, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5 - Sulfonic acid esters and the like can be mentioned as preferred examples.
【００３０】酸生成化合物の添加量は好ましくはアルカ
リ可溶性樹脂１００重量部に対して５〜１００重量部で
あり、特に好ましくは１０〜５０重量部である。５重量
部未満であると、放射線を吸収して生成するカルボン酸
の量が少なくなるので、放射線照射前後のアルカリ水溶
液に対する溶解度に差をつけることができず、パターニ
ングが困難となり、さらに後述するエポキシ化合物との
反応においても、関与するカルボン酸の量が少ないので
、形成したマイクロレンズの耐熱変形性に不具合が生じ
る恐れがある。また、１００重量部を超えると、短時間
の放射線照射では添加した酸生成化合物の大半が未だそ
のままの形で残存するため、アルカリ水溶液への不溶化
効果が高過ぎて現像することが困難となる。The amount of the acid-generating compound added is preferably 5 to 100 parts by weight, particularly preferably 10 to 50 parts by weight, per 100 parts by weight of the alkali-soluble resin. If the amount is less than 5 parts by weight, the amount of carboxylic acid produced by absorbing radiation will be small, making it impossible to differentiate the solubility in alkali aqueous solution before and after radiation irradiation, making patterning difficult, and furthermore, Also in the reaction with the compound, since the amount of carboxylic acid involved is small, there is a risk that the formed microlens will have a problem in heat deformation resistance. Furthermore, if the amount exceeds 100 parts by weight, most of the added acid-forming compound will still remain in the same form after short-time radiation irradiation, and the insolubilization effect in an aqueous alkaline solution will be too high, making it difficult to develop.
【００３１】（Ｃ）エポキシ化合物
エポキシ化合物は、放射線の照射により発生したカルボ
ン酸とマイクロレンズの加熱処理時に反応する化合物で
あり、カルボン酸との反応により熱硬化し、マイクロレ
ンズに耐熱性を付与するものである。従ってエポキシ化
合物は分子内に２個以上のエポキシ基を含有する必要が
あり、その例としては下記のものを例示できる。ビスフ
ェノールＡ型エポキシ樹脂市販品としては、例えばエピ
コート１００１、同１００２、同１００３、同１００４
、同１００７、同１００９、同１０１０（油化シェルエ
ポキシ（株）製）；ビスフェノールＦ型エポキシ樹脂市
販品としては、例えばエピコート８０７（油化シェルエ
ポキシ（株）製）ビスフェノールＡＤ型エポキシ樹脂；
フェノールノボラック型エポキシ樹脂市販品としては、
例えばエピコート１５２、同１５４（油化シェルエポキ
シ（株）製）、ＥＰＰＮ−２０１、同２０２（日本化薬
（株）製）；クレゾールノボラック型エポキシ樹脂市販
品としては、例えばＥＯＣＮ−１０２Ｓ、同１０３Ｓ、
同１０４Ｓ、同１０２０、同１０２５、同１０２７（日
本化薬（株）製）；エピコート１８０Ｓ７５（油化シェ
ルエポキシ（株）製）；環状脂肪族エポキシ樹脂市販品
としては、例えばＣＹ−１７５、同１７７、同１７９（
ＣＩＢＡ−ＧＥＩＧＹ社製）、ＥＲＬ−４２３４、同４
２９９、同４２２１、同４２０６（Ｕ．Ｃ．Ｃ．社製）
；グリシジルエステル系エポキシ樹脂市販品としては、
例えばショーダイン５０８（昭和電工（株）製）、アラ
ルダイトＣＹ−１８２、同１９２、同１８４（ＣＩＢＡ
−ＧＥＩＧＹ社製）、エピクロン２００、同４００（大
日本インキ（株）製）、エピコート８７１、同８７２（
油化シェルエポキシ（株）製）、ＥＤ−５６６１、同５
６６２（セラニーズコーティング（株）製）；(C) Epoxy compound The epoxy compound is a compound that reacts with carboxylic acid generated by radiation irradiation during heat treatment of the microlens, and is thermally cured by the reaction with the carboxylic acid, imparting heat resistance to the microlens. It is something to do. Therefore, the epoxy compound must contain two or more epoxy groups in the molecule, examples of which include the following. Examples of commercially available bisphenol A epoxy resins include Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004.
, 1007, 1009, 1010 (manufactured by Yuka Shell Epoxy Co., Ltd.); Commercially available bisphenol F-type epoxy resins include, for example, Epicote 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) and bisphenol AD-type epoxy resin;
Commercially available phenol novolac type epoxy resins include:
For example, EPPN-152, EPPN-154 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPPN-201, EPPN-202 (manufactured by Nippon Kayaku Co., Ltd.); commercially available cresol novolac type epoxy resins include, for example, EOCN-102S, EPPN-103S. ,
104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.); Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd.); Commercially available cycloaliphatic epoxy resins include, for example, CY-175, 177, 179 (
CIBA-GEIGY), ERL-4234, same 4
299, 4221, 4206 (manufactured by U.C.C.)
; Commercially available glycidyl ester epoxy resins include:
For example, Shodyne 508 (manufactured by Showa Denko K.K.), Araldite CY-182, Araldite CY-192, Araldite CY-184 (CIBA
-GEIGY Co., Ltd.), Epicron 200, 400 (Dainippon Ink Co., Ltd.), Epicron 871, 872 (manufactured by Dainippon Ink Co., Ltd.)
Yuka Shell Epoxy Co., Ltd.), ED-5661, ED-5
662 (manufactured by Celanese Coating Co., Ltd.);
【００３
２】グリシジルアミン系エポキシ樹脂市販品としては、
例えばテトラグリシジルジアミノジフェニルメタン、ト
リグリシジル−パラ−アミノフェノール、トリグリシジ
ル−メタ−アミノフェノール、ジグリシジルアニリン、
ジグリシジルトルイジン、テトラグリシジルメタキシリ
レンジアミン、ジグリシジルトリブロムアニリン、テト
ラグリシジルビスアミノメチルシクロヘキサン；複素環
式エポキシ樹脂市販品としては、例えばアラルダイトＰ
Ｔ８１０（ＣＩＢＡ−ＧＥＩＧＹ社製）、エピコートＲ
ＸＥ−１５（油化シェルエポキシ（株）製）、ＥＰＩＴ
ＥＣ（日産化学（株）製）等を挙げることができる。003
2] Commercially available glycidylamine epoxy resins include:
For example, tetraglycidyldiaminodiphenylmethane, triglycidyl-para-aminophenol, triglycidyl-meta-aminophenol, diglycidylaniline,
Diglycidyl toluidine, tetraglycidyl metaxylylene diamine, diglycidyl tribromoaniline, tetraglycidyl bisaminomethyl cyclohexane; Commercially available heterocyclic epoxy resins include, for example, Araldite P.
T810 (manufactured by CIBA-GEIGY), Epicote R
XE-15 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPIT
Examples include EC (manufactured by Nissan Chemical Co., Ltd.).
【００３３】また、ここに挙げたエポキシ化合物の多く
は高分子量体であるが、本発明に用いるエポキシ化合物
としては、分子量によって制限されるものではなく、例
えばビスフェノールＡあるいはビスフェノールＦのジグ
リシジルエーテルの如き低分子量体でも使用することが
できる。Furthermore, although many of the epoxy compounds listed here are high molecular weight compounds, the epoxy compounds used in the present invention are not limited by molecular weight; for example, diglycidyl ether of bisphenol A or bisphenol F can be used. It is also possible to use low molecular weight substances such as.
【００３４】この中で加熱処理後も着色しにくい点から
、フェノールノボラック型エポキシ樹脂、クルゾールノ
ボラック型エポキシ樹脂、環状脂肪族エポキシ樹脂、グ
リシジルエステル系エポキシ樹脂が好ましい。これらエ
ポキシ化合物の使用量は酸生成化合物（Ｂ）に対して、
好ましくは１〜１００重量部より好ましくは２〜２０重
量部である。Among these, phenol novolac type epoxy resins, crusol novolac type epoxy resins, cycloaliphatic epoxy resins, and glycidyl ester type epoxy resins are preferred since they are less likely to be colored even after heat treatment. The amount of these epoxy compounds used is based on the acid generating compound (B).
Preferably it is 1 to 100 parts by weight, more preferably 2 to 20 parts by weight.
【００３５】１重量部未満では、酸生成化合物に放射線
を照射することにより生成するカルボン酸との反応が十
分に進行し難く、また形成したマイクロレンズの耐熱変
形性が十分なものとなり難くなる。また１００重量部を
超えると、組成物全体としての融点が低下してしまい、
マイクロレンズを作製する際に行う加熱処理の温度範囲
を広くすることができ難くなる。If the amount is less than 1 part by weight, the reaction with the carboxylic acid produced by irradiating the acid-generating compound with radiation will be difficult to proceed sufficiently, and the formed microlens will be difficult to have sufficient heat deformation resistance. Moreover, if it exceeds 100 parts by weight, the melting point of the composition as a whole will decrease,
This makes it difficult to widen the temperature range of heat treatment performed when manufacturing microlenses.
【００３６】（Ｄ）その他の配合剤
本発明の組成物においては、界面活性剤を配合すること
もできる。界面活性剤としては、例えば、ＢＭ−１００
０、ＢＭ−１１００（ＢＭ Ｃｈｅｍｉｅ社製）、メ
ガファックＦ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ
１８３（大日本インキ化学工業（株）製）、フロラード
ＦＣ−１３５、同ＦＣ−１７０Ｃ、同ＦＣ−４３０、同
ＦＣ−４３１（住友スリーエム（株）製）、サーフロン
Ｓ−１１２、同Ｓ−１１３、同Ｓ−１３１、同Ｓ−１４
１、同Ｓ−１４５（旭硝子（株）製）等の名称で市販さ
れているフッ素系界面活性剤を使用することができる。
これらの界面活性剤の使用量は、アルカリ可溶樹脂（Ａ
）１００重量部あたり好ましくは０．００５〜５重量部
、より好ましくは０．００１〜２重量部の範囲である。(D) Other additives The composition of the present invention may also contain surfactants. As the surfactant, for example, BM-100
0, BM-1100 (manufactured by BM Chemie), Megafac F142D, Megafac F172, F173, F
183 (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Florado FC-135, Florado FC-170C, Florado FC-430, Florado FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, Florado S-113 , S-131, S-14
1. A fluorine-based surfactant commercially available under the name S-145 (manufactured by Asahi Glass Co., Ltd.) can be used. The amount of these surfactants used is based on the alkali-soluble resin (A
) It is preferably in the range of 0.005 to 5 parts by weight, more preferably 0.001 to 2 parts by weight per 100 parts by weight.
【００３７】（感放射線性樹脂組成物の調製）本発明の
組成物は、上述した各成分を均一に混合することによっ
て容易に調製することができる。また、適当な溶媒に溶
解させて溶液の形で使用に供される。用いる溶媒として
は、アルカリ可溶性樹脂、酸生成化合物およびエポキシ
化合物等の成分を均一に溶解させることができ、かつ各
成分と反応しないものが用いられる。かかる溶媒として
は、例えばメタノール、エタノール等のアルコール類；
テトラヒドロフラン等のエーテル類；エチレングリコー
ルモノメチルエーテル、エチレングリコールモノエチル
エーテル等のグリコールエーテル類；メチルセロソルブ
アセテート、エチルセロソルブアセテート等のエチレン
グリコールアルキルエーテルアセテート類；ジエチレン
グリコールモノメチルエーテル、ジエチレングリコール
モノエチルエーテル、ジエチレングリコールジメチルエ
ーテル等のジエチレングリコール類；プロピレングリコ
ールメチルエーテルアセテート、プロピレングリコール
プロピルエーテルアセテート等のプロピレングリコール
アルキルエーテルアセテート類；トルエン、キシレン等
の芳香族炭化水素類；メチルエチルケトン、シクロヘキ
サノン、４−ヒドロキシ−４−メチル−２−ペンタノン
等のケトン類；２−ヒドロキシプロピオン酸エチル、２
−ヒドロキシ−２−メチルプロピオン酸エチル、２−ヒ
ドロキシ−２−メチルプロピオン酸エチル、エトキシ酢
酸エチル、ヒドロキシ酢酸エチル、２−ヒドロキシ−３
−メチルブタン酸メチル、３−メトキシプロピオン酸メ
チル、３−メトキシプロピオン酸エチル、３−エトキシ
プロピオン酸エチル、３−エトキシプロピオン酸メチル
、酢酸エチル、酢酸ブチル等のエステル類を用いること
ができる。(Preparation of radiation-sensitive resin composition) The composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components. It can also be used in the form of a solution by dissolving it in a suitable solvent. The solvent used is one that can uniformly dissolve components such as the alkali-soluble resin, acid-generating compound, and epoxy compound, and that does not react with each component. Examples of such solvents include alcohols such as methanol and ethanol;
Ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, etc. diethylene glycols; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone Ketones such as; ethyl 2-hydroxypropionate, 2
-ethyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3
Esters such as methyl -methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, and butyl acetate can be used.
【００３８】さらに、Ｎ−メチルホルムアミド、Ｎ，Ｎ
−ジメチルホルムアミド、Ｎ−メチルホルムアニリド、
Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミ
ド、Ｎ−メチルピロリドン、ジメチルスルホキシド、ベ
ンジルエチルエーテル、ジヘキシルエーテル、アセトニ
ルアセトン、イソホロン、カプロン酸、カプリル酸、１
−オクタノール、１−ノナノール、ベンジルアルコール
、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、
マレイン酸ジエチル、γ−ブチロラクトン、炭酸エチレ
ン、炭酸プロピレン、フェニルセロソルブアセテート等
の高沸点溶剤を添加することもできる。Furthermore, N-methylformamide, N,N
-dimethylformamide, N-methylformanilide,
N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate,
High boiling point solvents such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.
【００３９】これらの溶剤の中では、一般的には塗膜の
形成のし易さからいって、エチレングリコールモノエチ
ルエーテル等のグリコールエーテル類；エチルセロソル
ブアセテート等のエチレングリコールアルキルエーテル
アセテート類；２−ヒドロキシプロピオン酸エチル等の
エステル類；ジエチレングリコールモノメチルエーテル
等のジエチレングリコール類が好適である。Among these solvents, generally speaking, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; - Esters such as ethyl hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether are preferred.
【００４０】また組成物の溶液の調製にあたっては、例
えばアルカリ可溶性樹脂の溶液、酸生成化合物の溶液お
よびエポキシ化合物の溶液との３種類の溶液を調製して
おき、使用直前にこれら溶液を所定の割合で混合するこ
ともできる。以上のようにして調製した組成物は、例え
ば孔径０．２μｍのミリポアフィルター等を用いて濾過
した後、使用に供する。[0040] Further, in preparing the solution of the composition, for example, three kinds of solutions are prepared: a solution of an alkali-soluble resin, a solution of an acid-generating compound, and a solution of an epoxy compound. They can also be mixed in proportion. The composition prepared as described above is used after being filtered using, for example, a Millipore filter with a pore size of 0.2 μm.
【００４１】（マイクロレンズの作製方法）本発明にお
いては、上述した組成物の溶液を、所定の基体表面に塗
布し、加熱により溶媒を除去することによって所望の塗
膜を形成することができる。基体表面への塗布方法は特
に限定されず、例えばスプレー法、ロールコート法、回
転塗布法等の各種の方法を採用することができる。(Method for Producing a Microlens) In the present invention, a desired coating film can be formed by applying a solution of the above-described composition onto the surface of a predetermined substrate and removing the solvent by heating. The method of coating the surface of the substrate is not particularly limited, and various methods such as a spray method, a roll coating method, and a spin coating method can be employed.
【００４２】なお、本発明の組成物の塗膜の加熱条件は
、各成分の具体的種類、配合割合等によっても異なるが
、通常は７０〜９０℃で５〜１５分間程度である。次に
、得られた塗膜に所定のパターンのマスクを介して、例
えば紫外線を照射した後、アルカリ水溶液を用いて現像
し、レジストパターンを形成させる。本発明における現
像液としては、例えば水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナ
トリウム、アンモニア水、エチルアミン、ｎ−プロピル
アミン、ジエチルアミン、ジ−ｎ−プロピルアミン、ト
リエチルアミン、メチルジエチルアミン、ジメチルエタ
ノールアミン、トリエタノールアミン、テトラメチルア
ンモニウムヒドロキシド、テトラエチルアンモニウムヒ
ドロキシド、ピロール、ピペリジン、１，８−ジアザビ
シクロ（５，４，０）−７−ウンデセン、１，５−ジア
ザビシクロ（４，３，０）−５−ノナン等のアルカリ類
の水溶液を使用することができる。また上記アルカリ類
の水溶液にメタノール、エタノール等の水溶性有機溶媒
や界面活性剤を適当量添加した水溶液を現像液として使
用することもできる。[0042] The heating conditions for the coating film of the composition of the present invention vary depending on the specific types and proportions of each component, but are usually at 70 to 90°C for about 5 to 15 minutes. Next, the resulting coating film is irradiated with, for example, ultraviolet rays through a mask with a predetermined pattern, and then developed using an alkaline aqueous solution to form a resist pattern. Examples of the developer in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo(5,4,0)-7-undecene, 1,5-diazabicyclo(4, An aqueous solution of an alkali such as 3,0)-5-nonane can be used. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above-mentioned alkali can also be used as the developer.
【００４３】現像時間は好ましくは３０〜１８０秒間で
あり、また現像の手法は液盛り法、ディッピング法等の
いずれでもよい。現像後は、流水洗浄を３０〜９０秒間
行い、圧縮空気や圧縮窒素で風乾させることによって、
レジストパターンを形成させることができる。その後、
例えば紫外線を照射することによってレジストパターン
中に残存している酸生成化合物をカルボン酸化合物に変
化させる。そして、ホットプレート、オーブン等の加熱
装置を用いて、所定の温度例えば１００〜１７０℃で、
所定の時間例えばホットプレート上なら２〜１０分間、
オーブン中ならば１５〜４５分間、加熱処理をすること
によってマイクロレンズを得ることができる。The developing time is preferably 30 to 180 seconds, and the developing method may be a piling method, a dipping method, or the like. After development, wash with running water for 30 to 90 seconds and air dry with compressed air or compressed nitrogen.
A resist pattern can be formed. after that,
For example, by irradiating with ultraviolet rays, the acid generating compound remaining in the resist pattern is converted into a carboxylic acid compound. Then, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 100 to 170 °C,
For a specified period of time, for example 2 to 10 minutes on a hot plate,
Microlenses can be obtained by heat treatment for 15 to 45 minutes in an oven.
【００４４】[0044]
【実施例】次に実施例をあげて本発明をさらに具体的に
説明するが、本発明はこれらの実施例によって何ら制約
されるものではない。また、特にことわりの無い限り、
％は重量％を示す。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited in any way by these Examples. Also, unless otherwise noted,
% indicates weight %.
【００４５】合成例１
フラスコ内を窒素置換した後、２，２′−アゾビスイソ
ブチロニトリル９．０ｇを溶解したジエチレングリコー
ルジメチルエーテル溶液４５９．０ｇを仕込んだ。引き
続きスチレン３７．５ｇ、メチルメタクリレート７５．
０およびメタクリル酸３７．５ｇを仕込んだ後、ゆるや
かに攪拌を始めた。８０℃で重合を開始し、この温度を
８時間保持した後、９０℃で１時間加熱させて重合を終
結させた。Synthesis Example 1 After purging the inside of the flask with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution containing 9.0 g of 2,2'-azobisisobutyronitrile was charged. Subsequently, 37.5 g of styrene and 75 g of methyl methacrylate were added.
After charging 0 and 37.5 g of methacrylic acid, gentle stirring was started. Polymerization was started at 80°C, maintained at this temperature for 8 hours, and then heated at 90°C for 1 hour to terminate the polymerization.
【００４６】その後、反応生成溶液を多量の水に滴下し
反応物を凝固させた。この凝固物を水洗後、テトラヒド
ロフラン２００ｇに再溶解し、多量の水で再度、凝固さ
せた。この再溶解−凝固操作を計３回行った後、得られ
た凝固物を６０℃で４８時間真空乾燥し、目的とする共
重合体を得た。その後固形分濃度が２５重量％になるよ
うにジエチレングリコールを用いて共重合体溶液とした
。Thereafter, the reaction product solution was dropped into a large amount of water to solidify the reaction product. After washing this coagulated product with water, it was redissolved in 200 g of tetrahydrofuran and coagulated again with a large amount of water. After performing this redissolution-coagulation operation three times in total, the obtained coagulated product was vacuum-dried at 60° C. for 48 hours to obtain the desired copolymer. Thereafter, a copolymer solution was prepared using diethylene glycol so that the solid content concentration was 25% by weight.
【００４７】合成例２
耐圧ガラスびん内を窒素置換した後、２，２′−アゾビ
スイソブチロニトリル４．５ｇを溶解したジエチレング
リコールジメチルエーテル溶液２２９．５ｇを仕込んだ
。引き続きスチレン１３．０５ｇ、メチルメタクリレー
ト２７．０８ｇ、メタクリル酸１３．５０ｇを仕込んだ
後、１，３−ブタジエンを８．０３ｇ仕込んだ。７０℃
で重合を開始し、この温度を８時間保持した後、９０℃
で１時間加熱させて重合を終結させた。その後、合成例
１と同様にして共重合体溶液を得た。Synthesis Example 2 After purging the inside of a pressure-resistant glass bottle with nitrogen, 229.5 g of a diethylene glycol dimethyl ether solution containing 4.5 g of 2,2'-azobisisobutyronitrile was charged. Subsequently, 13.05 g of styrene, 27.08 g of methyl methacrylate, and 13.50 g of methacrylic acid were charged, and then 8.03 g of 1,3-butadiene was charged. 70℃
Polymerization was started at 90°C, and after maintaining this temperature for 8 hours,
The polymerization was terminated by heating for 1 hour. Thereafter, a copolymer solution was obtained in the same manner as in Synthesis Example 1.
【００４８】合成例３
フラスコ内を窒素置換した後、２，２′−アゾビスイソ
ブチロニトリル４．５ｇ、無水マレイン酸４５．０ｇを
溶解したジエチレングリコールジメチルエーテル溶液５
０８．５ｇを仕込んだ。引き続きα−メチルスチレン１
３５．０ｇを仕込みゆるやかに攪拌を始めた。７０℃で
重合を開始し、この温度を５時間保持した後、９０℃で
１時間加熱させて重合を終結させた。その後、合成例１
と同様にして共重合体溶液を得た。Synthesis Example 3 After purging the inside of the flask with nitrogen, diethylene glycol dimethyl ether solution 5 in which 4.5 g of 2,2'-azobisisobutyronitrile and 45.0 g of maleic anhydride were dissolved was added.
08.5g was charged. Continuing with α-methylstyrene 1
Added 35.0 g and started stirring gently. Polymerization was started at 70°C, maintained at this temperature for 5 hours, and then heated at 90°C for 1 hour to terminate the polymerization. After that, Synthesis Example 1
A copolymer solution was obtained in the same manner as above.
【００４９】合成例４
フラスコにフェノール１０２ｇ、ｔ−ブチルフェノール
１８ｇ、３７重量％ホルムアルデヒド水溶液９２ｍｌお
よびシュウ酸０．０４ｇを仕込んだ。次いで、攪拌しな
がら、フラスコを油浴に浸し、内温を１００℃に保持し
ながら、３時間３０分反応させた。その後、油浴温度を
１８０℃まで上げ、同時にフラスコ内を減圧にして、水
、未反応のフェノール、ｔ−ブチルフェノール、ホルム
アルデヒドおよびシュウ酸を除去し、ノボラック樹脂を
回収した。Synthesis Example 4 A flask was charged with 102 g of phenol, 18 g of t-butylphenol, 92 ml of a 37% by weight formaldehyde aqueous solution, and 0.04 g of oxalic acid. Next, the flask was immersed in an oil bath while stirring, and the reaction was carried out for 3 hours and 30 minutes while maintaining the internal temperature at 100°C. Thereafter, the oil bath temperature was raised to 180° C., and at the same time the pressure inside the flask was reduced to remove water, unreacted phenol, t-butylphenol, formaldehyde, and oxalic acid, and recover the novolac resin.
【００５０】実施例１
（１）感放射線液の調製
合成例１で得られた共重合体溶液１００ｇ（共重合体２
５ｇ）をジエチレングリコールジメチルエーテル１３．
６４ｇで希釈したのち、４，４′−［１−［４−（１−
（４−ヒドロキシフェニル）−１−メチルエチル）フェ
ニル］エチリデン］ジフェノールの１，２−ナフトキノ
ンジアジド−５−スルホン酸エステル（平均エステル化
率６６．７モル％）１０．０ｇおよびｏ−クレゾールノ
ボラック型エポキシ樹脂ＥＯＣＮ−１０２０（日本化薬
（株）社製）１．２５ｇを溶解し、孔径０．２２μｍの
ミリポアフィルターで濾過して感放射線液（１）を調製
した。Example 1 (1) Preparation of radiation-sensitive liquid 100 g of the copolymer solution obtained in Synthesis Example 1 (Copolymer 2
5g) of diethylene glycol dimethyl ether13.
After diluting with 64 g, 4,4'-[1-[4-(1-
10.0 g of 1,2-naphthoquinonediazide-5-sulfonic acid ester of (4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]diphenol (average esterification rate 66.7 mol%) and o-cresol novolak 1.25 g of type epoxy resin EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) was dissolved and filtered through a Millipore filter with a pore size of 0.22 μm to prepare a radiation-sensitive solution (1).
【００５１】（２）塗膜の形成
ヘキサメチルジシラザン処理したシリコン酸化膜を有す
るウェハー上にスピンナーで上記感放射線液（１）を塗
布したのち、８０℃で１０分間オーブン中でプレベーク
して膜厚２．０μｍのレジスト膜を形成した。(2) Formation of a coating film After applying the radiation-sensitive liquid (1) using a spinner onto a wafer having a silicon oxide film treated with hexamethyldisilazane, the film is prebaked in an oven at 80° C. for 10 minutes. A resist film with a thickness of 2.0 μm was formed.
【００５２】（３）マイクロレンズの作製上記（２）で
得られたレジスト膜に所定のパターンマスクをウェハー
に密着し、３６５ｎｍでの光強度が１０ｍＪ／ｃｍ２で
ある紫外線を３０秒間照射した。次いでテトラメチルア
ンモニウムヒドロキシド０．１２％水溶液で２５℃で２
分間現像した後、超純水で１分間リンスしたところ線巾
０．８μｍのスペースを解像できた。その後、同じ露光
装置を用いて５０秒間全面露光し、クリーンオーブン中
で表１に示すレンズ形成可能温度で３０分間加熱したと
ころ、巾５．０μｍのマイクロレンズに形成することが
できた。このレンズを用いて耐熱変形性を評価し、結果
を表１に示した（以下、実施例２〜１０において同じ）
。(3) Preparation of microlenses A predetermined pattern mask was closely attached to the wafer on the resist film obtained in (2) above, and ultraviolet light having a light intensity of 10 mJ/cm 2 at 365 nm was irradiated for 30 seconds. Then, at 25°C, diluted with a 0.12% aqueous solution of tetramethylammonium hydroxide.
After developing for a minute, the film was rinsed with ultrapure water for one minute, and a space with a line width of 0.8 μm could be resolved. Thereafter, the entire surface was exposed for 50 seconds using the same exposure device, and heated in a clean oven for 30 minutes at a temperature at which lens formation is possible as shown in Table 1, and a microlens with a width of 5.0 μm could be formed. The heat deformation resistance was evaluated using this lens, and the results are shown in Table 1 (hereinafter, the same applies to Examples 2 to 10).
.
【００５３】なお、耐熱変形性は次のようにして評価し
た。
耐熱変形性：得られたマイクロレンズを１７０℃で３時
間の加熱後、スペースの線巾が加熱前の線巾の８０％を
越えた場合を○、５０〜８０％の場合を△、５０％未満
の場合を×とした。[0053] The heat deformation resistance was evaluated as follows. Heat deformation resistance: After heating the obtained microlens at 170°C for 3 hours, ○ if the line width of the space exceeds 80% of the line width before heating, △ if 50% to 80%, 50% Cases less than 100% were marked as ×.
【００５４】（４）透明性の評価
上記（２）において、ヘキサメチルジシラザン処理した
シリコン酸化膜を有するウェハーの代わりに、透明基板
（コーニング７０５９：コーニング社製）を用いた以外
は上記（２）と同様にレジスト膜を形成した。次いで、
テトラメチルアンモニウムヒドロキシド水溶液で現像処
理した後、超純水で１分間リンスした。さらに５０秒間
全面露光し、線巾５．０μｍのパターンをレンズに形成
することができる温度でクリーンオーブンを用いて加熱
し、さらに２００℃で１時間加熱した。得られたマイク
ロレンズを有する透明基板を分光光度計（１５０−２０
型ダブルビーム；（株）日立製作所製）を用いて４００
〜８００ｎｍの透過率を測定し、最低透過率が９５％を
越えた場合を○、９０〜９５％の場合を△、９０％未満
の場合を×とした。結果を表１に示した（以下、実施例
２〜１０において同じ）。(4) Evaluation of transparency In the above (2), except that a transparent substrate (Corning 7059, manufactured by Corning Inc.) was used instead of the wafer having a silicon oxide film treated with hexamethyldisilazane. ) A resist film was formed in the same manner. Then,
After developing with a tetramethylammonium hydroxide aqueous solution, the film was rinsed with ultrapure water for 1 minute. The entire surface was further exposed to light for 50 seconds, heated in a clean oven at a temperature at which a pattern with a line width of 5.0 μm could be formed on the lens, and further heated at 200° C. for 1 hour. The obtained transparent substrate with microlenses was measured with a spectrophotometer (150-20
400 using a type double beam (manufactured by Hitachi, Ltd.)
The transmittance of ~800 nm was measured, and the case where the minimum transmittance exceeded 95% was rated as ◯, the case of 90 to 95% as △, and the case of less than 90% as ×. The results are shown in Table 1 (hereinafter the same applies to Examples 2 to 10).
【００５５】実施例２
合成例１で得られた共重合体溶液の代わりに合成例２で
得られた共重合体溶液を使用して、実施例１に準じて調
製、評価したところテトラメチルアンモニウムヒドロキ
シド０．２０％水溶液で線巾１．０μｍのスペースを解
像できた。また、１３０〜１４０℃の温度での加熱によ
り同様なマイクロレンズに形成することができた。Example 2 The copolymer solution obtained in Synthesis Example 2 was used in place of the copolymer solution obtained in Synthesis Example 1, and as a result of preparation and evaluation according to Example 1, tetramethylammonium A space with a line width of 1.0 μm could be resolved using a 0.20% hydroxide aqueous solution. Further, similar microlenses could be formed by heating at a temperature of 130 to 140°C.
【００５６】実施例３
合成例１で得られた共重合体溶液の代わりに合成例３で
得られた共重合体溶液を使用して、実施例１に準じて調
製・評価したところ、紫外線を１０秒間照射した後、テ
トラメチルアンモニウムヒドロキシド２．０％水溶液で
線巾０．８μｍのスペースを解像できた。また、１５０
〜１６０℃の温度での加熱により同様なマイクロレンズ
に形成することができた。Example 3 The copolymer solution obtained in Synthesis Example 3 was used in place of the copolymer solution obtained in Synthesis Example 1, and the results were prepared and evaluated in accordance with Example 1. After irradiation for 10 seconds, a space with a line width of 0.8 μm could be resolved with a 2.0% aqueous solution of tetramethylammonium hydroxide. Also, 150
Similar microlenses could be formed by heating at temperatures of ~160°C.
【００５７】実施例４
（１）合成例４で得られたノボラック樹脂３７．０ｇと
４，４′−［１−［４−（１−（４−ヒドロキシフェニ
ル）−１−メチルエチル）フェニル］エチリデン］ジフ
ェノールの１，２−ナフトキノンジアジド−５−スルホ
ン酸エステル（平均エステル化率６６．７モル％）１４
．８ｇおよびｏ−クレゾールノボラック型エポキシ樹脂
ＥＯＣＮ−１０２０（日本化薬（株）製）１．８５ｇを
、エチルセロソルブアセテート１３１．１８ｇにて溶解
した。その後、孔径０．２２μｍのミリポアフィルター
で濾過して感放射線液を調製した。Example 4 (1) 37.0 g of the novolac resin obtained in Synthesis Example 4 and 4,4'-[1-[4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl] 1,2-naphthoquinonediazide-5-sulfonic acid ester of diphenol (average esterification rate 66.7 mol%) 14
．． 8 g and 1.85 g of o-cresol novolac type epoxy resin EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.) were dissolved in 131.18 g of ethyl cellosolve acetate. Thereafter, the mixture was filtered through a Millipore filter with a pore size of 0.22 μm to prepare a radiation-sensitive liquid.
【００５８】（２）実施例１に準じて評価したところ、
紫外線を１０秒間照射した後、テトラメチルアンモニウ
ムヒドロキシド２．２％水溶液で、線巾０．６μｍのス
ペースを解像できた。また、１１０〜１３０℃の温度で
の加熱により同様なマイクロレンズに形成することがで
きた。(2) When evaluated according to Example 1,
After irradiating with ultraviolet rays for 10 seconds, a space with a line width of 0.6 μm could be resolved with a 2.2% aqueous solution of tetramethylammonium hydroxide. Further, similar microlenses could be formed by heating at a temperature of 110 to 130°C.
【００５９】実施例５
実施例１で使用した４，４′−［１−［４−（１−（４
−ヒドロキシフェニル）−１−メチルエチル）フェニル
］エチリデン］ジフェノールの１，２−ナフトキノンジ
アジド−５−スルホン酸エステルの代わりに、ｍ−クレ
ゾール／ｐ−クレゾール＝６／４（重量比）を用いて得
られた平均核体数３．９のノボラック樹脂と１，２−ナ
フトキノンジアジド−５−スルホン酸エステル（平均エ
ステル化率５８．０モル％）１０．０ｇを用いて実施例
１に準じて調製・評価したところ、３０秒間の紫外線照
射後、テトラメチルアンモニウムヒドロキシド０．１６
％水溶液で線巾１．０μｍのスペースを解像することが
できた。また、１５０〜１７０℃の温度での加熱により
同様なマイクロレンズに形成することができた。Example 5 4,4'-[1-[4-(1-(4
m-cresol/p-cresol = 6/4 (weight ratio) was used instead of 1,2-naphthoquinonediazide-5-sulfonic acid ester of -hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]diphenol. According to Example 1, using a novolak resin with an average number of nuclei of 3.9 obtained by When prepared and evaluated, it was found that after 30 seconds of ultraviolet irradiation, tetramethylammonium hydroxide was 0.16
% aqueous solution, it was possible to resolve a space with a line width of 1.0 μm. Further, similar microlenses could be formed by heating at a temperature of 150 to 170°C.
【００６０】実施例６
実施例１で使用した４，４′−［１−［４−（１−（４
−ヒドロキシフェニル）−１−メチルエチル）フェニル
］エチリデン］ジフェノールの１，２−ナフトキノンジ
アジド−５−スルホン酸エステルの代わりに２，３，４
，４′−テトラヒドロキシベンゾフェノンの１，２−ナ
フトキノンジアジド−５−スルホン酸エステル（平均エ
ステル化率７５モル％）１０．０ｇを用いて実施例１に
準じて調製・評価したところ、３０秒間の紫外線照射後
、テトラメチルアンモニウムヒドロキシド０．１４％水
溶液で線巾０．８μｍのスペースを解像することができ
た。また、１４０〜１５０℃の温度での加熱により同様
なマイクロレンズに形成することができた。Example 6 4,4'-[1-[4-(1-(4
2,3,4-hydroxyphenyl)-1-methylethyl)phenyl]ethylidene]diphenol instead of 1,2-naphthoquinonediazide-5-sulfonic acid ester
, 4'-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonic acid ester (average esterification rate 75 mol%) was prepared and evaluated according to Example 1. After irradiation with ultraviolet rays, a space with a line width of 0.8 μm could be resolved with a 0.14% aqueous solution of tetramethylammonium hydroxide. Further, similar microlenses could be formed by heating at a temperature of 140 to 150°C.
【００６１】実施例７
実施例１のｏ−クレゾールノボラック型エポキシ樹脂の
代わりにビスフェノールＡ型エポキシ樹脂エピコート８
２８（油化シェルエポキシ（株）製）１．２５ｇを用い
て実施例１に準じて調製・評価したところ、３０秒間の
紫外線照射後、テトラメチルアンモニウムヒドロキシド
０．１８％水溶液で線巾１．２μｍのスペースを解像す
ることができた。また、１４０〜１６０℃の温度での加
熱により同様なマイクロレンズに形成することができた
。Example 7 Bisphenol A type epoxy resin Epicoat 8 was used instead of the o-cresol novolac type epoxy resin in Example 1.
28 (manufactured by Yuka Shell Epoxy Co., Ltd.) according to Example 1. After irradiation with ultraviolet rays for 30 seconds, a 0.18% aqueous solution of tetramethylammonium hydroxide It was possible to resolve a space of .2 μm. Moreover, similar microlenses could be formed by heating at a temperature of 140 to 160°C.
【００６２】実施例８
実施例１のｏ−クレゾールノボラック型エポキシ樹脂の
代わりにビスフェノールＦ型エポキシ樹脂エピコート８
１５（油化シェルエポキシ（株）製）１．２５ｇを用い
て実施例１に準じて調製・評価したところ、３０秒間の
紫外線照射後、テトラメチルアンモニウムヒドロキシド
０．１４％水溶液で線巾１．０μｍのスペースを解像す
ることができた。また、１３０〜１４０℃の温度での加
熱により同様なマイクロレンズに形成することができた
。Example 8 Bisphenol F type epoxy resin Epicoat 8 was used instead of the o-cresol novolac type epoxy resin of Example 1.
15 (manufactured by Yuka Shell Epoxy Co., Ltd.) according to Example 1 was prepared and evaluated. After 30 seconds of ultraviolet irradiation, a 0.14% aqueous solution of tetramethylammonium hydroxide It was possible to resolve a space of .0 μm. Further, similar microlenses could be formed by heating at a temperature of 130 to 140°C.
【００６３】実施例９
実施例１のｏ−クレゾールノボラック型エポキシ樹脂の
代わりに環状脂肪族エポキシ樹脂ＣＹ−１７９（ＣＩＢ
Ａ−ＧＥＩＧＹ（株）製）１．２５ｇを用いて実施例１
に準じて調製・評価したところ、３０秒間の紫外線照射
後、テトラメチルアンモニウムヒドロキシド０．２０％
水溶液で線巾０．８μｍのスペースを解像することがで
きた。また、１５０〜１６０℃の温度での加熱により同
様なマイクロレンズに形成することができた。Example 9 Cycloaliphatic epoxy resin CY-179 (CIB
Example 1 using 1.25 g of A-GEIGY Co., Ltd.
When prepared and evaluated according to
It was possible to resolve a space with a line width of 0.8 μm using the aqueous solution. Further, similar microlenses could be formed by heating at a temperature of 150 to 160°C.
【００６４】実施例１０
実施例１のｏ−クレゾールノボラック型エポキシ樹脂の
代わりにアラルダイトＣＹ１８４（ＣＩＢＡ−ＧＥＩＧ
Ｙ（株）製）１．２５ｇを用いて実施例１に準じて調製
・評価したところ、３０秒間の紫外線照射後、テトラメ
チルアンモニウムヒドロキシド０．１６％水溶液で線巾
１．０μｍのスペースを解像することができた。また、
１２０〜１４０℃の温度での加熱により同様なマイクロ
レンズに形成することができた。Example 10 Araldite CY184 (CIBA-GEIG
When prepared and evaluated in accordance with Example 1 using 1.25 g of 1.25 g of Y Co., Ltd., after 30 seconds of ultraviolet irradiation, a space with a line width of 1.0 μm was filled with a 0.16% aqueous solution of tetramethylammonium hydroxide. I was able to resolve it. Also,
A similar microlens could be formed by heating at a temperature of 120-140°C.
【００６５】[0065]
【表１】[Table 1]
【００６６】比較例１〜７
実施例１〜７に示した組成物の成分であるエポキシ化合
物を加えないで、同様に合成・調製・評価を行った。そ
の結果を表２にまとめた。Comparative Examples 1 to 7 Synthesis, preparation, and evaluation were carried out in the same manner as in Examples 1 to 7 without adding the epoxy compound that was a component of the composition. The results are summarized in Table 2.
【００６７】[0067]
【表２】[Table 2]
【００６８】[0068]
【発明の効果】本発明によれば、所望の形状のマイクロ
レンズを作製でき、耐熱変形性および透明性に優れたレ
ンズを与えることのできるマイクロレンズ用樹脂組成物
が提供される。According to the present invention, there is provided a resin composition for microlenses, which can produce microlenses of desired shapes and provide lenses with excellent heat deformation resistance and transparency.
Claims (1)
放射線性酸生成化合物および（Ｃ）エポキシ基を分子内
に少くとも２個有する化合物、を含有することを特徴と
するマイクロレンズ用感放射線性樹脂組成物。1. A microlens composition comprising (A) an alkali-soluble resin, (B) a radiation-sensitive acid-generating compound, and (C) a compound having at least two epoxy groups in the molecule. Radioactive resin composition.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15372991A JP3241399B2 (en) | 1991-05-30 | 1991-05-30 | Radiation-sensitive resin composition for microlenses |
| US07/888,635 US5362597A (en) | 1991-05-30 | 1992-05-27 | Radiation-sensitive resin composition comprising an epoxy-containing alkali-soluble resin and a naphthoquinone diazide sulfonic acid ester |
| EP92304963A EP0520626B1 (en) | 1991-05-30 | 1992-05-29 | Radiation-sensitive resin composition |
| KR1019920009256A KR100232372B1 (en) | 1991-05-30 | 1992-05-29 | Radiation-sensitive resin composition |
| DE69228574T DE69228574T2 (en) | 1991-05-30 | 1992-05-29 | Radiation sensitive resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15372991A JP3241399B2 (en) | 1991-05-30 | 1991-05-30 | Radiation-sensitive resin composition for microlenses |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04352101A true JPH04352101A (en) | 1992-12-07 |
| JP3241399B2 JP3241399B2 (en) | 2001-12-25 |
Family
ID=15568824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15372991A Expired - Lifetime JP3241399B2 (en) | 1991-05-30 | 1991-05-30 | Radiation-sensitive resin composition for microlenses |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3241399B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002029493A1 (en) * | 2000-09-29 | 2002-04-11 | Nippon Zeon Co., Ltd. | Photoresist composition for forming insulation film, insulation film for organic electroluminescence element and method for its formation |
| WO2003029898A1 (en) * | 2001-09-27 | 2003-04-10 | Clariant International Ltd. | Photosensitive resin composition |
| JP2007079553A (en) * | 2005-08-19 | 2007-03-29 | Jsr Corp | Positive photosensitive insulating resin composition, cured material thereof, and circuit board |
| WO2008069159A1 (en) * | 2006-11-28 | 2008-06-12 | Jsr Corporation | Method for producing microlens |
| WO2008143095A1 (en) * | 2007-05-17 | 2008-11-27 | Nissan Chemical Industries, Ltd. | Photosensitive resin and process for producing microlens |
| CN103450389A (en) * | 2012-05-31 | 2013-12-18 | 株式会社Lg化学 | New polymer and coloring composition comprising the same |
| JP2015179166A (en) * | 2014-03-19 | 2015-10-08 | ナガセケムテックス株式会社 | positive photosensitive resin composition |
| KR20160074528A (en) | 2013-10-21 | 2016-06-28 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive-type photosensitive resin composition |
| KR20170092542A (en) | 2014-12-04 | 2017-08-11 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive-acting photosensitive resin composition |
-
1991
- 1991-05-30 JP JP15372991A patent/JP3241399B2/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002029493A1 (en) * | 2000-09-29 | 2002-04-11 | Nippon Zeon Co., Ltd. | Photoresist composition for forming insulation film, insulation film for organic electroluminescence element and method for its formation |
| US7008883B2 (en) | 2000-09-29 | 2006-03-07 | Zeon Corporation | Photoresist composition for forming an insulation film, insulation film for organic electroluminescence devices and process for producing the insulation film |
| WO2003029898A1 (en) * | 2001-09-27 | 2003-04-10 | Clariant International Ltd. | Photosensitive resin composition |
| JP2007079553A (en) * | 2005-08-19 | 2007-03-29 | Jsr Corp | Positive photosensitive insulating resin composition, cured material thereof, and circuit board |
| WO2008069159A1 (en) * | 2006-11-28 | 2008-06-12 | Jsr Corporation | Method for producing microlens |
| TWI480594B (en) * | 2006-11-28 | 2015-04-11 | Jsr Corp | The manufacturing method of microlenses |
| JP5093525B2 (en) * | 2007-05-17 | 2012-12-12 | 日産化学工業株式会社 | Photosensitive resin and microlens manufacturing method |
| JP2012247801A (en) * | 2007-05-17 | 2012-12-13 | Nissan Chem Ind Ltd | Positive resist composition |
| US8940470B2 (en) | 2007-05-17 | 2015-01-27 | Nissan Chemical Industries, Inc. | Photosensitive resin and process for producing microlens |
| WO2008143095A1 (en) * | 2007-05-17 | 2008-11-27 | Nissan Chemical Industries, Ltd. | Photosensitive resin and process for producing microlens |
| CN103450389A (en) * | 2012-05-31 | 2013-12-18 | 株式会社Lg化学 | New polymer and coloring composition comprising the same |
| CN103450389B (en) * | 2012-05-31 | 2016-05-25 | 株式会社Lg化学 | Polymer and the coloured composition that comprises it |
| KR20160074528A (en) | 2013-10-21 | 2016-06-28 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive-type photosensitive resin composition |
| JP2015179166A (en) * | 2014-03-19 | 2015-10-08 | ナガセケムテックス株式会社 | positive photosensitive resin composition |
| KR20170092542A (en) | 2014-12-04 | 2017-08-11 | 닛산 가가쿠 고교 가부시키 가이샤 | Positive-acting photosensitive resin composition |
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