JPH03233457A - Photosensitive resin composition - Google Patents
Photosensitive resin compositionInfo
- Publication number
- JPH03233457A JPH03233457A JP4566890A JP4566890A JPH03233457A JP H03233457 A JPH03233457 A JP H03233457A JP 4566890 A JP4566890 A JP 4566890A JP 4566890 A JP4566890 A JP 4566890A JP H03233457 A JPH03233457 A JP H03233457A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- group
- denotes
- acrylate
- photosensitive resin
- 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
- 239000011342 resin composition Substances 0.000 title claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims abstract description 7
- 229920002647 polyamide Polymers 0.000 claims abstract description 7
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 14
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 4
- 238000004321 preservation Methods 0.000 abstract 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 21
- 229920005575 poly(amic acid) Polymers 0.000 description 18
- 229920001721 polyimide Polymers 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- -1 acrylate compound Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002966 varnish Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000009878 intermolecular interaction Effects 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- 229940013085 2-diethylaminoethanol Drugs 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 208000017983 photosensitivity disease Diseases 0.000 description 2
- 231100000434 photosensitization Toxicity 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- WKCYFSZDBICRKL-UHFFFAOYSA-N 3-(diethylamino)propan-1-ol Chemical compound CCN(CC)CCCO WKCYFSZDBICRKL-UHFFFAOYSA-N 0.000 description 1
- TYKLCAKICHXQNE-UHFFFAOYSA-N 3-[(2,3-dicarboxyphenyl)methyl]phthalic acid Chemical compound OC(=O)C1=CC=CC(CC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O TYKLCAKICHXQNE-UHFFFAOYSA-N 0.000 description 1
- NLSQENXHYZSNFE-UHFFFAOYSA-N 3-amino-5-phenylpentane Chemical compound CCC(N)CCC1=CC=CC=C1 NLSQENXHYZSNFE-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- QQWWWAQUMVHHQN-UHFFFAOYSA-N 4-(4-amino-4-phenylcyclohexa-1,5-dien-1-yl)aniline Chemical group C1=CC(N)=CC=C1C1=CCC(N)(C=2C=CC=CC=2)C=C1 QQWWWAQUMVHHQN-UHFFFAOYSA-N 0.000 description 1
- DUMUYWBRRIUWHI-UHFFFAOYSA-N 4-(4-aminophenyl)phosphanylaniline Chemical compound C1=CC(N)=CC=C1PC1=CC=C(N)C=C1 DUMUYWBRRIUWHI-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- LBNFPUAJWZYIOQ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-methylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C)C1=CC=C(N)C=C1 LBNFPUAJWZYIOQ-UHFFFAOYSA-N 0.000 description 1
- DUZDWKQSIJVSMY-UHFFFAOYSA-N 5-[4-(6-amino-2-methylhexan-2-yl)phenyl]-5-methylhexan-1-amine Chemical compound NCCCCC(C)(C)C1=CC=C(C(C)(C)CCCCN)C=C1 DUZDWKQSIJVSMY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は可視光あるいは紫外光に対する感度などの光学
特性及び現像特性に優れ、しかも耐熱性に優れた感光性
樹脂i!Ji戒物に放物るものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a photosensitive resin i! which has excellent optical properties such as sensitivity to visible light or ultraviolet light, and development properties, as well as excellent heat resistance. It is something that is thrown into the Ji precepts.
(従来技術)
従来、半導体素子の表面保護膜、眉間絶縁膜などには、
耐熱性が優れ、また卓越した電気絶縁性、機械強度など
を有するポリイミドが用いられているが、ポリイミドパ
ターンを作成する繁雑な工程を簡略化する為にポリイミ
ド自身に感光性を付与する技術が最近注目を集めている
。(Prior art) Conventionally, surface protection films of semiconductor elements, glabellar insulating films, etc.
Polyimide is used because it has excellent heat resistance, as well as excellent electrical insulation and mechanical strength, but recently technology has been developed to impart photosensitivity to polyimide itself in order to simplify the complicated process of creating polyimide patterns. It is attracting attention.
例えば、下式
で示される様な構造のエステル基で感光性基を付与した
ポリイミド前駆体1戒物(特開昭55−30207号公
報)あるいはポリアミック酸に化学線により2量化また
は重合可能な炭素−炭素二重結合及びアミノ基又は、そ
の四級化塩を含む化合物を添加した組成物(例えば特開
昭54−145794号公報)などが知られている。For example, a polyimide precursor with a photosensitive group added with an ester group as shown in the following formula (Japanese Unexamined Patent Publication No. 55-30207), or a polyamic acid with carbon that can be dimerized or polymerized by actinic radiation. - Compositions containing a compound containing a carbon double bond and an amino group or a quaternized salt thereof (for example, JP-A No. 145794/1984) are known.
これらは、いずれも適当な有機溶剤に溶解し、ワニス状
態で塗布、乾燥した後、フォトマスクを介して紫外線照
射し、現像、リンス処理して所望のパターンを得、さら
に加熱処理する事によりポリイミド被膜としている。All of these are dissolved in an appropriate organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and further heat-treated to form a polyimide. It is a coating.
感光性を付与したポリイミドを使用するとパターン作成
工程の簡素化効果があるだけでなく、毒性の強いエツチ
ング液を使用しなくてすむので安全でかつ、公害上も優
れておりポリイミドの感光性化は今後、−層重要な技術
となる事が期待されている。Using polyimide with photosensitization not only simplifies the pattern creation process, but also eliminates the need to use highly toxic etching solutions, making it safer and less polluting. It is expected that this technology will become an important technology in the future.
しかし、かかる従来の感光化技術を適用するとエステル
基で感光性基を付与したボリイξド前駆体組放物では、
感光性基が熱硬化時に飛散しにくいために硬化後のフィ
ルムの耐熱性が低いものしか得られず、半導体工業で使
用することは難しかった。However, when such conventional photosensitization technology is applied, the polyamide ξ-do precursor parabolite to which a photosensitive group is added with an ester group,
Since the photosensitive groups are difficult to scatter during heat curing, only films with low heat resistance after curing can be obtained, making it difficult to use in the semiconductor industry.
又ポリアミック酸に化学線により2量化または重合可能
な炭素−炭素二重結合及びアミノ基または、その四級化
塩を含む化合物を添加した&ll戒物放物、赤外線を照
射しても著しく感度が低く、又保管時にワニスの粘度が
大きく変化するために半導体工業で通常用いられている
製造工程で使用するには不十分であった。In addition, compounds containing carbon-carbon double bonds and amino groups that can be dimerized or polymerized by actinic radiation, or quaternized salts thereof are added to polyamic acids, and the sensitivity is extremely low even when irradiated with infrared rays. The viscosity of the varnish was low and the viscosity of the varnish changed greatly during storage, making it insufficient for use in manufacturing processes commonly used in the semiconductor industry.
(発明が解決しようとする課題)
本発明の目的とするところは、ポリアミド酸化合物中に
カルボキシル基を有するアクリレート化合物と光増感剤
を配合することにより、高感度の光硬化性を有し、また
保管時に配合物の粘度変化がなく、さらに硬化後の被膜
が耐熱性、耐熱サイクル性、耐熱ショック性、耐湿性な
どが優れた感光性樹脂組成物を提供するにある。(Problems to be Solved by the Invention) The object of the present invention is to have high sensitivity photocurability by blending an acrylate compound having a carboxyl group and a photosensitizer in a polyamic acid compound. Another object of the present invention is to provide a photosensitive resin composition in which the viscosity of the compound does not change during storage, and the film after curing has excellent heat resistance, heat cycle resistance, heat shock resistance, moisture resistance, etc.
<tJ、Hを解決するための手段)
本発明者らは従来技術では克服できなかったこれらの問
題を解決するため鋭意検討した結果(A)下記式(1)
(1)
(式中R+ 、Rtは同−又は異なる芳香族環状基を、
R8は−CJ4N(CH+)z又は−CJaN(CJs
)2を、mは6以上200以下の整数を示す)で示され
るボリア旦ド酸化合物
アクリル基又はメタクリル基を1または2個有する下記
式(ff)のアクリレート
(■)
(式中Xは−H又は−CHコ基、Yはフェニル基、Zは
−CJ4−、−Csll1.O,Pは1又は2を示す)
(C)吸収極大波長(λwax )が330〜555n
11である増感剤を必須成分とする
ことにより高信頼性を有する感光性樹脂組成物を得るこ
とが可能であるとの知見を得、本発明を完成するに至っ
た。<Means for solving tJ, H) The present inventors have conducted extensive studies to solve these problems that could not be overcome with conventional techniques. (A) As a result of the following formula (1) (1) (wherein R+, Rt is the same or different aromatic cyclic group,
R8 is -CJ4N(CH+)z or -CJaN(CJs
) 2, m is an integer of 6 or more and 200 or less) An acrylate of the following formula (ff) having one or two acrylic or methacrylic groups (■) (wherein X is - H or -CH co group, Y is phenyl group, Z is -CJ4-, -Csll1.O, P is 1 or 2)
(C) Maximum absorption wavelength (λwax) is 330 to 555n
The present invention was completed based on the finding that it is possible to obtain a highly reliable photosensitive resin composition by using the sensitizer No. 11 as an essential component.
(作 用)
本発明におけるボリア藁ド酸化合物(A)は、ボリイく
ド被膜の耐熱性を向上させるために熱硬化後に芳香族ポ
リイミドとなる事が望ましい、このようなポリアミド酸
化合物(A)は、T−ブチロラクトン、N−メチル−2
−ピロリドン、N、N−ジメチルアセトアミドなどの極
性溶媒中、芳香族テトラカルボン酸無水物にアミノアル
コールを反応させて得られるテトラカルボン酸のジエス
テル体と、ジアミンの縮合により台底される。感度を向
上させるためには、ポリアミド酸化合物(A)は高分子
量になることが好ましく、そのため反応温度は−20°
C〜50℃であることが好ましく一10℃から30℃が
さらに好ましい、またジカルボン酸類とジアミソ類のモ
ル化は0.8〜1.1であることが好ましい。(Function) The boria straw acid compound (A) in the present invention is a polyamide acid compound (A) that preferably becomes an aromatic polyimide after thermosetting in order to improve the heat resistance of the boria straw acid coating. is T-butyrolactone, N-methyl-2
- The bottom is formed by condensation of a diester of a tetracarboxylic acid obtained by reacting an aromatic tetracarboxylic anhydride with an amino alcohol in a polar solvent such as pyrrolidone or N,N-dimethylacetamide, and a diamine. In order to improve sensitivity, it is preferable that the polyamic acid compound (A) has a high molecular weight, so the reaction temperature is -20°
The temperature is preferably from C to 50°C, more preferably from -10°C to 30°C, and the molarization of the dicarboxylic acids and diamisos is preferably from 0.8 to 1.1.
下記式(1)中の芳香族環状基R1,R2とは例えばベ
ンゼン環、
(I)
(式中R+ 、 Rzは同−又は異なる芳香族環状基を
、R3は−CJaN(CI+) z又は−CJ4N (
C2H4) zを、mは6以上200以上の整数を示す
)ナフタレン環などである。またmは6以下200以下
であることが好ましい。6未満だと感度が低下し、20
0を超えるものは工業的に合成が難しい。 上記式(1
)のポリアミド酸化合物を合成するのに用いる芳香族テ
トラカルボン酸二無水物としては次の様な酸無水物が挙
げられる。ピロメリット酸二無水物、3,3°、4.4
′−ベンゾフェノンテトラカルボン酸二無水物、2.3
,6.7−ナフタレンテトラカルボン酸二無水物、3.
3’、4.4°−ジフェニルテトラカルボン酸二無水物
、2.2’ 、3,3. ’−ジフェニルテトラカルボ
ン酸二無水酸二無水物、1,2,5,6.−ナフタレン
テトラカルボン酸二無水物、2.2−ビス(3,4−ジ
カルボキシジフェニル)エーテルニ無水物、ナフタレン
−1,2,4,5テトラカルボン酸二無水物、ナフタレ
ン−1,4,58、−テトラカルボン酸二無水物、4.
8−ジメチル−1゜2.3,5.6,7.−へキサヒド
ロナフタレン−1,2,5,6テトラカルポン酸二無水
物、2.6.−ジクロロナフタレン、1.4,5.8−
テトラカルボン酸二無水物、2.7−シクロロナフタレ
ンー1.4,5.8−テトラカルボン酸二無水物、フェ
ナンスレン−1,2,9,10−7−トラカルボン酸二
無水物、ピロリジン−2,3,4,5,−テトラカルボ
ン酸二無水物、ピラジン−2,3,5,6,−テトラカ
ルボン酸二無水物、2.2−ビス(2,5−ジカルボキ
シフェニル)プロパンニ無水物、1.l−ビス(2゜3
−ジカルボキシフェニル)エタンニ無水物、l、1−ビ
ス(3,4−ジカルボキシフェニル)エタンニ無水物、
ビス(2,3−ジカルボキシフェニル)メタンニ無水物
、ビス(3,4−ジカルボキシフェニル)スルホンニ無
水物、ベンゼン−1,2,3,4−ブタンテトラカルボ
ン酸二無水物、チオフェン−2,3,4,5−テトラカ
ルボン酸二無水物などである。The aromatic cyclic groups R1 and R2 in the following formula (1) are, for example, a benzene ring, (I) (in the formula, R+ and Rz are the same or different aromatic cyclic groups, and R3 is -CJaN(CI+)z or - CJ4N (
C2H4) where z is an integer of 6 or more and 200 or more) naphthalene ring, etc. Moreover, it is preferable that m is 6 or less and 200 or less. If it is less than 6, the sensitivity will decrease and 20
Those exceeding 0 are difficult to synthesize industrially. The above formula (1
Examples of the aromatic tetracarboxylic dianhydride used to synthesize the polyamic acid compound (2) include the following acid anhydrides. Pyromellitic dianhydride, 3,3°, 4.4
'-benzophenonetetracarboxylic dianhydride, 2.3
, 6.7-naphthalenetetracarboxylic dianhydride, 3.
3', 4.4°-diphenyltetracarboxylic dianhydride, 2.2', 3,3. '-Diphenyltetracarboxylic dianhydride, 1,2,5,6. -Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4,5tetracarboxylic dianhydride, naphthalene-1,4,58 , -tetracarboxylic dianhydride, 4.
8-dimethyl-1°2.3,5.6,7. -hexahydronaphthalene-1,2,5,6 tetracarboxylic dianhydride, 2.6. -dichloronaphthalene, 1.4,5.8-
Tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-7-tracarboxylic dianhydride, pyrrolidine -2,3,4,5,-tetracarboxylic dianhydride, pyrazine-2,3,5,6,-tetracarboxylic dianhydride, 2,2-bis(2,5-dicarboxyphenyl)propani Anhydrous, 1. l-bis(2゜3
-dicarboxyphenyl)ethane dianhydride, l,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
Bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-butanetetracarboxylic dianhydride, thiophene-2, 3,4,5-tetracarboxylic dianhydride and the like.
上記芳香族テトラカルボン酸二無水物の他に各種特性付
与する為にシリコーン系テトラカルボン酸二無水物や脂
肪族系テトラカルボン酸二無水物も勿論併用することが
できる。In addition to the aromatic tetracarboxylic dianhydride mentioned above, silicone tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride can of course be used in combination to impart various properties.
また、ポリアミド酸化合物合成に使用するアミノアルコ
ールとしては2−ジメチルアミノエタノール、2−ジエ
チルアミノエタノール、3−ジメチルアミツブロバノー
ル、3−ジエチルアミノプロパノールなどであるがこれ
に限定されない。In addition, examples of amino alcohols used in the synthesis of polyamic acid compounds include, but are not limited to, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylamitubrobanol, and 3-diethylaminopropanol.
また、ポリアミド酸化合物合成に使用する芳香族ジアミ
ン成分は一種類でも、二種類以上の混合物でもかまわな
いが用いられる芳香族ジアミンとしては訃フェニレンジ
アミン、p−フ二二レンジアミン、4.4’−ジアミノ
ジフェニルプロパン、4.4’−ジアミノジフェニルメ
タン、ベンジジン、4.4゜ジアミノジフェニルスルフ
ィド、4,4°−ジアミノフェニルスルホン、3.3′
−ジアミノジフェニル明細書の浄書
スルホン、4,4゛−ジアミノジフェニルエーテル、3
.3°−ジアミノジフェニルエーテル、4.4’−ジア
ミノ−p−テルフェニル、2.6−ジアミツピリジン、
ビス(4−アミノフェニル)ホスフィンオキシト、ビス
(4−アミノフェニル)−N−メチルアミン、1゜5−
ジアミノナフタレン、3.3“−ジメチル−4,4°−
ジアミノビフェニル、3.3゛−ジメトキシベンジジン
、2.4−ビス(β−アミノ−(−ブチル)−トルエン
、ビス(p−β−アミノ−L−ブチルフェニル)エーテ
ル、p−ビス(2−メチル−4−アミノペンチル)ベン
ゼン、p−ビス(l、1−ジメチル−5−アミノペンチ
ル)ベンゼン、2.4−ジアミノトルエン、トキシリレ
ンジアミン、p−キシリレンジアミンなどである。Further, the aromatic diamine component used in the synthesis of the polyamic acid compound may be one type or a mixture of two or more types, but the aromatic diamines used include phenylene diamine, p-phenyl diamine, 4.4' -diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4.4°diaminodiphenyl sulfide, 4,4°-diaminophenyl sulfone, 3.3'
- Diaminodiphenyl specifications sulfone, 4,4'-diaminodiphenyl ether, 3
.. 3°-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl, 2,6-diamitupyridine,
Bis(4-aminophenyl)phosphine oxyto, bis(4-aminophenyl)-N-methylamine, 1゜5-
Diaminonaphthalene, 3.3"-dimethyl-4,4°-
Diaminobiphenyl, 3.3'-dimethoxybenzidine, 2.4-bis(β-amino-(-butyl)-toluene, bis(p-β-amino-L-butylphenyl)ether, p-bis(2-methyl) -4-aminopentyl)benzene, p-bis(l,1-dimethyl-5-aminopentyl)benzene, 2,4-diaminotoluene, toxylylenediamine, p-xylylenediamine, and the like.
本発明で使用するジアミン成分としては、上記の芳香族
ジアミンの他に各種特性を付与する為にシリコーン系ジ
アミンや脂肪族系ジアミンも勿論併用する事ができる。As the diamine component used in the present invention, in addition to the above-mentioned aromatic diamines, silicone diamines and aliphatic diamines can also be used in combination to impart various properties.
このようにして得られたポリアミド酸化合物は、ポリア
ミック酸のようなカルボキシル基がないために、分子間
相互作用がなく保存中のワニスの粘度安定性に優れてい
る。The polyamic acid compound thus obtained does not have a carboxyl group unlike polyamic acid, so there is no intermolecular interaction and the varnish has excellent viscosity stability during storage.
本発明におけるアクリレート(B)は下記式%式%
()
(式中Xは−H又は−CL基、Yはフェニル基、Zは−
C,l+、 −、〜Cs1la−,○、Pは1又は2を
示す)1分子中に1または2個のアクリル基またはメタ
クリル基とカルボン酸基を有するアクリレート化合物で
ある。アクリレートとしてはアクリル酸、メタクリル酸
、フタル酸エチル−2−アクリレート、フタル酸エチル
−2−メタクリレートフタル酸プロピル−2−アクリレ
ート、フタル酸プロピル−2−メタクリレートトリメリ
ン1−酸エチル−2−アクリレート、トリメリット酸エ
チル−2−メタクリレートピロメリット酸ジエチル−2
−ジアクリレート、ピロメリット酸ジエチル−2−ジメ
タクリレートなどであるが、これらに限定さない。The acrylate (B) in the present invention has the following formula % formula % () (wherein X is -H or -CL group, Y is phenyl group, Z is -
C, l+, -, ~Cs1la-, ○, P indicates 1 or 2) It is an acrylate compound having one or two acrylic or methacrylic groups and a carboxylic acid group in one molecule. The acrylates include acrylic acid, methacrylic acid, ethyl phthalate-2-acrylate, ethyl phthalate-2-methacrylate, propyl phthalate-2-acrylate, propyl phthalate-2-methacrylate, trimerin-1-ethyl-2-acrylate, Ethyl trimellitate-2-methacrylate Diethyl pyromellitate-2
- diacrylate, diethyl pyromellitate-2-dimethacrylate, etc., but are not limited to these.
又本発明における増感剤(C)は330〜500nmに
明細書:の浄:)
吸収極大波長(λmaχ)を持つ化合物である。The sensitizer (C) in the present invention is a compound having a maximum absorption wavelength (λmax) of 330 to 500 nm.
l waxが33Or+m未満であると、ポリアミド酸
化合物のものに光が吸収されてしまい光反応ができない
ので好ましくない、又、500nmを超えると可視光で
光反応してしまい作業場所をンールドルームにするなど
のことが必要となり、その取扱い性が低下するので好ま
しくない0本発明の増感剤は例えば、
明細書の浄書
明細書の浄書
明細書の浄書
などであるがこれらに限定されない。If l wax is less than 33Or+m, light will be absorbed by the polyamic acid compound and no photoreaction will occur, which is undesirable.If it exceeds 500nm, photoreaction will occur with visible light, making the work place an abandoned room. Examples of the sensitizer of the present invention, which are not preferable because the handling thereof is deteriorated, include, but are not limited to, sensitizers of the present invention.
以下に本発明のMi戒放物使用法を述べる。The method of using the Mi Kaiboku of the present invention will be described below.
本発明の組成物、該IJl戒物生物中べての組成物を?
8解しうるl容媒に溶解して所定の基板上に塗布する。The composition of the present invention, the composition of all the IJl precepts?
The solution is dissolved in a medium that can be dissolved in water and applied onto a predetermined substrate.
上記溶媒としては極性溶媒が好ましく、例えばN−メチ
ル−ピロリドン、ジメチアセトアミド、γブチロラクト
ン、ジメチルホルムアミドなどである。The solvent is preferably a polar solvent, such as N-methyl-pyrrolidone, dimethiacetamide, γ-butyrolactone, or dimethylformamide.
またシリコンウェハ等の基板との密着性を高めにために
、例えばトリエトキシビニルシラン、トリ(メトキシエ
トキン)ビニルシラン、T−グリシドキンプロピルトリ
メトキシシラン等のシランカップリング剤を添加する。Further, in order to enhance adhesion to a substrate such as a silicon wafer, a silane coupling agent such as triethoxyvinylsilane, tri(methoxyethquin)vinylsilane, T-glycidquinpropyltrimethoxysilane is added.
基板上に塗布する方法としては、前記ようにして得られ
た溶液をスピンコータ、バーコータ、スクリーン印刷法
などで基板に塗布する。基板としては、金属、ガラス、
シリコン、ガラスエポキシなどである。As a method for coating the substrate, the solution obtained as described above is coated on the substrate using a spin coater, a bar coater, a screen printing method, or the like. Substrates include metal, glass,
These include silicone and glass epoxy.
次に、このようにして得られた塗膜を風乾、加熱乾燥、
真空乾燥などにより乾燥したのち、露光を行う、この際
、用いる活性光線としては、例えば可視光、紫外線、X
線、電子線などが挙げられ可視光と紫外線が好ましい。Next, the coating film obtained in this way is air-dried, heat-dried,
After drying by vacuum drying etc., exposure is performed.At this time, the active light used is, for example, visible light, ultraviolet light, X-rays, etc.
Rays, electron beams, etc. may be mentioned, with visible light and ultraviolet light being preferred.
このようにして露光した後、未照射部を除去すべく、浸
漬法やスプレー法などを用いて現像を行う、この除用い
る現像液としては例えば、N−メチルピロリドン、N、
N−ジメチルホルムアミド、N、 N−ジメチルアセト
アミド、ジメチルスルホキシドなどの非プロトン性極性
溶媒を単独で用いてもよいし、あるいはこれらに第2戒
分として、例えばエタノール、イソプロパツールなどの
アルコール、ヘキサン、シクロヘキサンなどの脂肪族炭
化水素、トルエン、キシレンなどの芳香族炭化水素化合
物などの溶媒を混合して用いてもよい、更に、現像直後
に前記第2成分として示したような溶媒でリンスするこ
とが好ましい。After exposure in this way, development is performed using a dipping method or a spray method to remove the unirradiated areas. Examples of developing solutions used for this removal include N-methylpyrrolidone, N,
Aprotic polar solvents such as N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide may be used alone, or they may be supplemented with alcohols such as ethanol, isopropanol, hexane, etc. as a secondary component. , aliphatic hydrocarbons such as cyclohexane, and aromatic hydrocarbon compounds such as toluene and xylene may be mixed and used.Furthermore, immediately after development, rinsing with a solvent such as that shown as the second component may be used. is preferred.
このようにして得られたポリアミドを主成分とする画像
を、硬化後レジスト、絶縁膜、保護膜等の用途に用いる
。The thus obtained image containing polyamide as a main component is used for applications such as a resist, an insulating film, and a protective film after being cured.
この際必要に応じて加熱による不要成分の除去、ポリア
ミドの化学構造の変換などの処理を行う。At this time, treatments such as removing unnecessary components by heating and converting the chemical structure of the polyamide are performed as necessary.
実施例 次に実施例による本発明を更に詳細に説明する。Example Next, the present invention will be explained in more detail using examples.
実施例1
ピロメリット酸無水物21.8g (0,1+of )
、2−ジメチルアミノエタノール36.8 g (0
,207ao乏)p−トルエンスルホン酸−水和物19
.0g (0,1mojりをN−メチル−2−ピロリド
ン200111中、室温で4時間反応させる0次にジメ
チルホルムアミド41.2g (0,2+wof)のN
−メチル−2−ピロリドン液をゆっくり滴下し、75分
間反応させる。Example 1 Pyromellitic anhydride 21.8g (0,1+of)
, 2-dimethylaminoethanol 36.8 g (0
, 207ao-poor) p-toluenesulfonic acid hydrate 19
.. 41.2 g (0,2 + wof) of N
-Methyl-2-pyrrolidone solution was slowly added dropwise and allowed to react for 75 minutes.
次に4,4°−ジアミノジフェニルエーテル18. (
0,911102)を加え、4時間反応させた後、沈澱
物を濾過し、濾液を52のエタノール中に加え黄白色の
ポリイミド酸化化合物を得た。このポリイミド酸化合物
100重量をN−メチル−2−ピロリドン400重量部
に溶解し、メチルメタクリレート80重量部と光増感剤
ミヒラーケトン5重量部を室温で3時間攪拌し、溶解、
混合した。Next, 4,4°-diaminodiphenyl ether18. (
After 4 hours of reaction, the precipitate was filtered, and the filtrate was added to ethanol (52) to obtain a yellow-white polyimide oxide compound. 100 parts by weight of this polyimide acid compound was dissolved in 400 parts by weight of N-methyl-2-pyrrolidone, 80 parts by weight of methyl methacrylate and 5 parts by weight of photosensitizer Michler's ketone were stirred at room temperature for 3 hours, and dissolved.
Mixed.
得られた溶液をアルミ板上にスピンナーで塗布し、乾燥
機により80’CI時間乾燥しフィルムを得た。The obtained solution was applied onto an aluminum plate using a spinner and dried using a drier for 80'CI hours to obtain a film.
このフィルムにコダック製フォトグラフィックステップ
タブレットN112,21ステツプ(上記ブレスケール
では、段数が一段増加するごとに透過光量が前段の1/
f2に減少するので現像後の被膜の残存段数が大きいも
の程感度が高い。)を重ね500mJ/cjの紫外線を
照射し、次いでN−メチルピロリドン60重量部、メタ
ノール40重量部の現像液を用いて現像、さらにイソプ
ロピルアルコールでリンスをしたところ200mJ/c
−の感度を有し高感度である事が判った。This film is coated with a Kodak Photographic Step Tablet N112, 21 Step (with the blur scale mentioned above, each step increase in the number of steps increases the amount of transmitted light by 1/2 of that of the previous step).
f2, so the larger the number of remaining stages of the film after development, the higher the sensitivity. ) were stacked and irradiated with 500 mJ/cj of ultraviolet rays, then developed using a developer containing 60 parts by weight of N-methylpyrrolidone and 40 parts by weight of methanol, and further rinsed with isopropyl alcohol to produce a result of 200 mJ/cj.
- It was found that the sensitivity was high.
次に凸版印刷製解像度測定用マスク(凸版テストチャー
トNcLl)を用い上記のバターニング実験と同様にし
て露光、現像を行ったところ、クランクの発生もなくか
つ膜厚の減少もほとんど認められなかった。Next, exposure and development were performed in the same manner as in the buttering experiment described above using a resolution measurement mask manufactured by Toppan Printing (Toppan Test Chart NcLl), and no cranking occurred and almost no decrease in film thickness was observed. .
またパターンは10μmの解像度を有していた。The pattern also had a resolution of 10 μm.
また、このポリイミドフィルムの熱分解開始製測定した
ところ、+5°Cの保管条件で30日間粘度変化はなか
った。Furthermore, when the polyimide film was measured for thermal decomposition, there was no change in viscosity for 30 days under storage conditions of +5°C.
このように得られた感光性樹脂&lI戒物放物感度であ
り、さらに高耐熱であり、またワニスの保存性にも優れ
ているという効果が同時に得られた。The photosensitive resin thus obtained had the following effects: high sensitivity, high heat resistance, and excellent varnish storage stability.
評価結果を第1表に示す。The evaluation results are shown in Table 1.
無水物32.2g (0,1mof ) 、 2−ジエ
チルアミノエタノール20.6g (0,2moI!、
) p−7zニレ7ジアミン10.8g (0,1ff
1al )を実施例1と同様にしてポリアミド酸化合物
を得た。32.2 g of anhydride (0.1 mof), 20.6 g of 2-diethylaminoethanol (0.2 moI!,
) p-7z elm 7 diamine 10.8g (0.1ff
1al) in the same manner as in Example 1 to obtain a polyamic acid compound.
このポリアミド酸化合物100重量部をT−フチロラク
トン300重量部に溶解し、さらにピロメリット酸ジエ
チル−2−ジアクリレート90重量部と、光増感剤ミヒ
ラーケトン5重量部を溶解、混合した。得られた感光性
樹脂&llll金物施例1と同様の方法で評価を行った
。結果を第1表に示す。100 parts by weight of this polyamic acid compound was dissolved in 300 parts by weight of T-phthyrolactone, and further 90 parts by weight of diethyl-2-diacrylate pyromellitate and 5 parts by weight of the photosensitizer Michler's ketone were dissolved and mixed. The resulting photosensitive resin & hardware was evaluated in the same manner as in Example 1. The results are shown in Table 1.
得られた感光性樹脂IJl威物は高感度で、さらに耐熱
性に優れていた。The resulting photosensitive resin IJl had high sensitivity and excellent heat resistance.
実施例3
2.3 * 3 ’+ 4 ’ −ジフェニルテトラカ
ルボン酸二無水物18.4g (0,1moj! )
、2−ジメチルアミノエタノール35.8g(0,20
1mof) 、p−7zニレ7ジアミン8.6g (0
,08mo j! )を実施例1と同様にしてポリアミ
ド酸化合物を得た。Example 3 2.3*3'+4'-diphenyltetracarboxylic dianhydride 18.4g (0.1moj!)
, 35.8 g of 2-dimethylaminoethanol (0,20
1mof), p-7z elm 7 diamine 8.6g (0
,08mo j! ) was carried out in the same manner as in Example 1 to obtain a polyamic acid compound.
このポリアミド酸化合物100重量部をN、N−ジメチ
ルアセトアミド200重量部に溶解し、さらにトリメリ
ット酸エチル−2−アクリレート70重量部と光増感剤
湾ヒラーケトンIO重量部を溶解、混法で評価を行った
。結果を第1表に示す。100 parts by weight of this polyamic acid compound was dissolved in 200 parts by weight of N,N-dimethylacetamide, and further 70 parts by weight of ethyl trimellitate-2-acrylate and parts by weight of the photosensitizer Bay Hiller Ketone IO were dissolved for evaluation by a mixed method. I did it. The results are shown in Table 1.
得られた感光性樹脂組成物は高感度でさらに耐熱性、ワ
ニスの保存性に優れている。The resulting photosensitive resin composition has high sensitivity, heat resistance, and varnish storage stability.
比較例1
3.3;4.4’−ベンゾフェノンテトラカルボン酸二
無水物290g (0,9鳳oi!、)、4,4°−ジ
アミノジフェニルエーテル200g (0,1monり
をN−メチルピロリドン中で反応させポリアミック酸溶
液を得た。Comparative Example 1 290 g of 3.3;4.4'-benzophenone tetracarboxylic dianhydride (0.9 oi!), 200 g of 4,4°-diaminodiphenyl ether (0.1 mon) in N-methylpyrrolidone. The reaction was carried out to obtain a polyamic acid solution.
得られたポリアミック酸溶液(ポリアミック酸の固形分
)100重量部に対しN、N−ジメチルアミノエチルメ
タクリレート80重量部とミヒラーケトン5重量部を室
温で3時間攪拌し、溶解、反応させ、感光性樹脂&[l
放物を得た。To 100 parts by weight of the obtained polyamic acid solution (solid content of polyamic acid), 80 parts by weight of N,N-dimethylaminoethyl methacrylate and 5 parts by weight of Michler's ketone were stirred at room temperature for 3 hours to dissolve and react, resulting in a photosensitive resin. &[l
I got a parabola.
得られた感光性樹脂&11戒物は、分子内にカルボキシ
ル基を有しているために、分子間相互作用が強く、保存
中に水分等の影響を受は粘度ガ大きく変化し、実用性の
低い事がわかった。The obtained photosensitive resin & 11 precepts has carboxyl groups in the molecule, so there is strong intermolecular interaction, and when it is affected by moisture etc. during storage, the viscosity changes greatly, making it impractical. I found it to be low.
比較例2
ピロメリット酸無水物21.8 g、2−ヒドロキシエ
チルメタクリレート21.0g、r−ブチロラクトン1
00dを位、水冷下、攪拌しながらピリジン17.0g
を加えた。常温で8時間攪拌した後、ジシクロへキシル
カルボジイミド41.2 gのγ−ブチロラクトン40
Jdの溶液を水冷下、10分間で加え、続いて4.4′
−ジアミノジフェニルエーテル16.0 gを15分間
で加えた水冷下、3時間攪拌し、沈澱を濾過した後、得
られた溶液を101のエタノールに加え黄白色の粉末を
得た。この粉末100重量部エチレア
ングリコールジ=クリレート40g、ミヒラーケトン0
.4g、ベンゾフェノン2.0g、ベンジルジメチルケ
クール4.0gをN−メチルピロリドン200gに溶解
して、感光性樹脂組成物を得た。Comparative Example 2 Pyromellitic anhydride 21.8 g, 2-hydroxyethyl methacrylate 21.0 g, r-butyrolactone 1
00d, add 17.0g of pyridine while stirring under water cooling.
added. After stirring at room temperature for 8 hours, 41.2 g of dicyclohexylcarbodiimide and 40 g of γ-butyrolactone were added.
A solution of Jd was added over 10 minutes under water cooling, followed by 4.4'
16.0 g of -diaminodiphenyl ether was added over 15 minutes, and the mixture was stirred for 3 hours under water cooling. After filtering the precipitate, the resulting solution was added to 101 ethanol to obtain a yellowish white powder. 100 parts by weight of this powder, 40 g of ethylene glycol di-acrylate, 0 Michler's ketone
.. 4g of benzophenone, 2.0g of benzophenone, and 4.0g of benzyldimethylkecoel were dissolved in 200g of N-methylpyrrolidone to obtain a photosensitive resin composition.
得られた感光性樹脂&IIt2物を実施例1と同様の方
法で加ニレパターンを形成した。このポリイミドフィル
ムの熱分解開始温度は330℃であった。An elm pattern was formed using the obtained photosensitive resin &IIt2 product in the same manner as in Example 1. The thermal decomposition initiation temperature of this polyimide film was 330°C.
このように得られた感光性樹脂&II威はポリイミド化
合物と感光基が共有結合で結合しているため、感光基が
飛散しずらく耐熱性が劣る。Since the photosensitive resin &II thus obtained has a polyimide compound and a photosensitive group bonded to each other through a covalent bond, the photosensitive group is difficult to scatter and has poor heat resistance.
評価結果を第1表に示す。The evaluation results are shown in Table 1.
(発明の効果)
アミノ基を有するアクリル化合物を配合して台底される
感光性ポリアミック酸は、分子間相互作用が強いために
、水分等の影響を受けやすく保存中の粘度が大きく変化
したり、またパターニングする為に光照射しても感度が
低いために半導体工業に適するには好ましくなかった。(Effect of the invention) Photosensitive polyamic acid, which is made by blending an acrylic compound with an amino group, has strong intermolecular interactions, so it is easily affected by moisture and the viscosity may change significantly during storage. Furthermore, even when irradiated with light for patterning, the sensitivity was low, making it unsuitable for the semiconductor industry.
しかるに本発明はポリイミド酸化合物(A)にカルボキ
シ基を含まないので分子間相互作用がなく、保存中の粘
度が安定している。また1〜2官能のアクリレート(B
)と吸収極大波長(λ−ax)が330〜500rrm
である増感剤(C)を配合するのでその結果極めて少な
い光照射量により架橋が生し高感度となる。However, in the present invention, since the polyimide acid compound (A) does not contain a carboxy group, there is no intermolecular interaction, and the viscosity during storage is stable. In addition, mono- to di-functional acrylate (B
) and maximum absorption wavelength (λ-ax) of 330 to 500 rrm
Since the sensitizer (C) is blended, as a result, crosslinking occurs with an extremely small amount of light irradiation, resulting in high sensitivity.
さらに熱硬化後のポリイミド被膜の耐熱性は、ポリイミ
ド化合物(A)中にアクリレート(B)を配合している
だけで、共有結合によるポリイミド骨格へのアクリレー
トの導入ではない為に、硬化時の加熱で容易に飛散し、
芳香族ポリイミド固有の耐熱性は保持され、高耐熱を示
すという非常に優れた効果が同時に得られる。Furthermore, the heat resistance of the polyimide film after thermosetting is determined by the heat resistance during curing, since the acrylate (B) is simply blended into the polyimide compound (A), and the acrylate is not introduced into the polyimide skeleton through covalent bonds. easily disperses,
The heat resistance inherent to aromatic polyimide is maintained, and the very excellent effect of exhibiting high heat resistance can be obtained at the same time.
Claims (1)
、R_3は−C_2H_4N(CH_3)_2又は−C
_2H_4N(C_2H_5)_2を、mは6以上20
0以下の整数を示す)で示されるポリアミド酸化合物 (B)アクリル酸、メタクリル酸又は1分子中にアクリ
ル基又はメタクリル基を1または2個有する下記式(I
I)のアクリレート ▲数式、化学式、表等があります▼(II) (式中Xは−H又は−CH_3基、Yはフェニル基、Z
は−C_2H_4−、−C_3H_6−、O、Pは1又
は2を示す)(C)吸収極大波長(λmax)が330
〜500nmである増感剤を必須成分とすることを特徴
とする感光性樹脂組成物。(1) (A) The following formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are the same or different aromatic cyclic groups, and R_3 is -C_2H_4N(CH_3)_2 or - C
_2H_4N(C_2H_5)_2, m is 6 or more 20
polyamide acid compound (B) represented by acrylic acid, methacrylic acid (representing an integer of 0 or less), or the following formula (I
Acrylate of I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, X is -H or -CH_3 group, Y is phenyl group, Z
-C_2H_4-, -C_3H_6-, O and P indicate 1 or 2) (C) Maximum absorption wavelength (λmax) is 330
A photosensitive resin composition comprising as an essential component a sensitizer having a wavelength of 500 nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4566890A JP2812774B2 (en) | 1989-12-12 | 1990-02-28 | Photosensitive resin composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP32051589 | 1989-12-12 | ||
JP1-320515 | 1989-12-12 | ||
JP4566890A JP2812774B2 (en) | 1989-12-12 | 1990-02-28 | Photosensitive resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03233457A true JPH03233457A (en) | 1991-10-17 |
JP2812774B2 JP2812774B2 (en) | 1998-10-22 |
Family
ID=26385715
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4566890A Expired - Lifetime JP2812774B2 (en) | 1989-12-12 | 1990-02-28 | Photosensitive resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2812774B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1152572A (en) * | 1997-08-08 | 1999-02-26 | Fujitsu Ltd | Photosensitive resin composition and pattern forming method by using the same |
CN108375874A (en) * | 2017-01-30 | 2018-08-07 | 旭化成株式会社 | The manufacturing method of photosensitive polymer combination, photoresist laminated body, the substrate for being formed with corrosion-resisting pattern and circuit board |
-
1990
- 1990-02-28 JP JP4566890A patent/JP2812774B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH1152572A (en) * | 1997-08-08 | 1999-02-26 | Fujitsu Ltd | Photosensitive resin composition and pattern forming method by using the same |
CN108375874A (en) * | 2017-01-30 | 2018-08-07 | 旭化成株式会社 | The manufacturing method of photosensitive polymer combination, photoresist laminated body, the substrate for being formed with corrosion-resisting pattern and circuit board |
CN108375874B (en) * | 2017-01-30 | 2021-10-22 | 旭化成株式会社 | Photosensitive resin composition, photosensitive resin laminate, substrate having resist pattern formed thereon, and method for producing circuit board |
Also Published As
Publication number | Publication date |
---|---|
JP2812774B2 (en) | 1998-10-22 |
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