JP5298675B2 - 感光性樹脂組成物、sawフィルタ及びその製造方法 - Google Patents
感光性樹脂組成物、sawフィルタ及びその製造方法 Download PDFInfo
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- JP5298675B2 JP5298675B2 JP2008180652A JP2008180652A JP5298675B2 JP 5298675 B2 JP5298675 B2 JP 5298675B2 JP 2008180652 A JP2008180652 A JP 2008180652A JP 2008180652 A JP2008180652 A JP 2008180652A JP 5298675 B2 JP5298675 B2 JP 5298675B2
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- photosensitive resin
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- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- XHXMPURWMSJENN-UHFFFAOYSA-N coumarin 480 Chemical compound C12=C3CCCN2CCCC1=CC1=C3OC(=O)C=C1C XHXMPURWMSJENN-UHFFFAOYSA-N 0.000 description 1
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- CURBACXRQKTCKZ-UHFFFAOYSA-N cyclobutane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)C(C(O)=O)C1C(O)=O CURBACXRQKTCKZ-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical group C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
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- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
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- 238000010894 electron beam technology Methods 0.000 description 1
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- 238000004299 exfoliation Methods 0.000 description 1
- 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 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 235000019382 gum benzoic Nutrition 0.000 description 1
- 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 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 238000006358 imidation reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- 229940086559 methyl benzoin Drugs 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N methyl cyclohexan-4-ol Natural products CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- ABMDIECEEGFXNC-UHFFFAOYSA-N n-ethylpropanamide Chemical compound CCNC(=O)CC ABMDIECEEGFXNC-UHFFFAOYSA-N 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- WSKHYOXDVZCOJP-UHFFFAOYSA-N naphthalene-1,6-diamine Chemical compound NC1=CC=CC2=CC(N)=CC=C21 WSKHYOXDVZCOJP-UHFFFAOYSA-N 0.000 description 1
- ZDWYJINCYGEEJB-UHFFFAOYSA-N naphthalene-1,7-diamine Chemical compound C1=CC=C(N)C2=CC(N)=CC=C21 ZDWYJINCYGEEJB-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- VQXBKCWOCJSIRT-UHFFFAOYSA-N octadecane-1,12-diamine Chemical compound CCCCCCC(N)CCCCCCCCCCCN VQXBKCWOCJSIRT-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- UMSVUULWTOXCQY-UHFFFAOYSA-N phenanthrene-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1C(O)=O UMSVUULWTOXCQY-UHFFFAOYSA-N 0.000 description 1
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- OFZAYFUSFITYES-UHFFFAOYSA-M trimethyl(2-phenylethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC1=CC=CC=C1 OFZAYFUSFITYES-UHFFFAOYSA-M 0.000 description 1
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Description
[式(1)中、Rはp価の有機基を示し、R’はそれぞれ独立に水素原子又はメチル基を示し、pは4〜6の整数を示す。]
[式(2)中、Ar1は4価の有機基を示し、Ar2は2価の有機基を示し、kは1以上の整数を示す。但し、Ar1が下記一般式(3)で表される4価の有機基、及び/又は、Ar2が下記一般式(4)で表わされる2価の有機基を示す。]
[式(3)中、Xは炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を示し、R1及びR2はそれぞれ独立に水素原子、炭素数1〜6のアルキル基又は炭素数1〜3のアルコキシ基を示し、m及びnはそれぞれ独立に1〜3の整数を示す。]
[式(4)中、Zは単結合又は2価の有機基を示し、Y1及びY2はそれぞれ独立に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を示す。]
[式(5)中、R3は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、qは1〜4の整数を示す。なお、qが2以上の場合、複数存在するR3は同一でも異なっていてもよい。]
[式(6)中、R4は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、rは1〜4の整数を示す。なお、rが2以上の場合、複数存在するR4は同一でも異なっていてもよい。]
[式(7)中、R5は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、sは1〜4の整数を示す。なお、sが2以上の場合、複数存在するR5は同一でも異なっていてもよい。]
本発明の感光性樹脂組成物は、(A)主鎖に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を有するポリアミック酸(以下、場合により「(A)成分」という)と、(B)重合性化合物(以下、場合により「(B)成分」という)と、(C)光重合開始剤(以下、場合により「(C)成分」という)と、を含有し、上記(B)重合性化合物が、分子内に4〜10のエチレン性不飽和基を有する重合性化合物を含むものである。以下、各成分について詳細に説明する。
[式(9)中、Y1及びY2はそれぞれ独立に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を示し、R3は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、qは1〜4の整数を示す。なお、qが2以上の場合、複数存在するR3は同一でも異なっていてもよい。]
[式(10)中、Y1及びY2はそれぞれ独立に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を示し、R4は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、rは1〜4の整数を示す。なお、rが2以上の場合、複数存在するR4は同一でも異なっていてもよい。]
[式(11)中、Y1及びY2はそれぞれ独立に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、上記炭素数に分岐部分の炭素数は含めない)を示し、R5は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、sは1〜4の整数を示す。なお、sが2以上の場合、複数存在するR5は同一でも異なっていてもよい。]
図1は、本発明のSAWフィルタの好適な一実施形態を示す模式断面図である。図1に示すように、SAWフィルタ100は、基板10と、該基板10上に形成された櫛形電極20と、基板10上の櫛形電極20が形成されている部分に中空空間を形成するためのリブ部30及び蓋部40と、櫛形電極20に電気的に接続された配線50と、を備えている。そして、リブ部30及び蓋部40は、本発明の感光性樹脂組成物からなる樹脂硬化物で構成されている。
(合成例1)
300mLの4つ口セパラブルフラスコに、バーサミン551(商品名、[3,4−ビス(1−アミノヘプチル)−6−ヘキシル−5−(1−オクテニル)]シクロヘキセン、コグニスジャパン社製)を15.73g(0.028mol)、4,4’−ジアミノジフェニルスルホン3.54g(0.014mol)、及び、N−メチルピロリドン30.0gを加えて室温で15分間攪拌した。次に、1,10−(デカメチレン)ビス(トリメリテート)二無水物22.24g(0.043mol)、及び、N−メチルピロリドン30.00gの混合溶液を15分間かけて添加した。添加終了後、得られた混合液を60℃まで昇温し、8時間攪拌することで、ポリアミック酸のN−メチルピロリドン溶液を得た。得られた溶液中の固形分は40質量%であり、ポリアミック酸の重量平均分子量は29000、分散度(重量平均分子量/数平均分子量)は1.7であった。なお、「バーサミン551」は、下記式(14)で表される化合物及び/又は下記式(14)で表される化合物の不飽和部が水添された化合物を含むジアミン化合物である。
300mLの4つ口セパラブルフラスコに、バーサミン551を19.61g(0.035mol)及びN−メチルピロリドン30gを加えて室温で15分間攪拌した。次に、1,10−(デカメチレン)ビス(トリメリテート)二無水物20.39g(0.039mol)、及び、N−メチルピロリドン30.00gの混合溶液を15分間かけて添加した。添加終了後、得られた混合液を60℃まで昇温し、8時間攪拌することで、ポリアミック酸のN−メチルピロリドン溶液を得た。得られた溶液中の固形分は40質量%であり、ポリアミック酸の重量平均分子量は33000、分散度(重量平均分子量/数平均分子量)は3.4であった。
300mLの4つ口セパラブルフラスコに、4,4’−ジアミノジフェニルスルホン12.89g(0.052mol)、γ−ブチロラクトン10.0gを加えて40℃で15分間攪拌した。次に、4,4’−オキシジフタル酸二無水和物16.44g(0.053mol)、及び、γ−ブチロラクトン29.66mLの混合溶液を15分間かけて添加した。添加終了後、60℃まで昇温し、5時間攪拌することで、ポリアミック酸のγ−ブチロラクトン溶液を得た。得られた溶液中の固形分は40質量%であり、ポリアミック酸の重量平均分子量は40000、分散度(重量平均分子量/数平均分子量)は2.0であった。
合成例1〜3で合成したポリアミック酸の重量平均分子量(Mw)及び数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィー(GPC)により測定し、標準ポリスチレンを用いた検量線により換算して求めた。GPCの条件を以下に示す。
検出器:LV4000 UV Detector(日立製作所社製、商品名)
ポンプ:L6000 Pump(日立製作所社製、商品名)
C−R4A Chromatopack(島津製作所製、商品名)
カラム:Gelpack GL−S300MDT−5(計2本)(日立化成工業社製、商品名)
溶離液:THF/DMF=1/1(容積比)+LiBr(0.03mol/L)+H3PO4(0.06mol/L)
流量:1mL/分
上記各合成例で合成した(A)ポリアミック酸の溶液、(B)重合性化合物、及び、(C)光重合開始剤を、それぞれ下記表1に示した配合割合(質量部)で混合し、実施例1〜6及び比較例1〜5の感光性樹脂組成物の溶液を得た。なお、表1中の数字は固形分の質量部を示している。また、表1中の各成分は、以下に示すものである。
ATM−4E(商品名、ペンタエリスリトールテトラアクリレート、新中村化学工業株式会社)、
A−TMPT(商品名、トリメチロールプロパントリアクリレート、新中村化学工業株式会社)、
ヒタロイド7660(商品名、酸変性エポキシアクリレート、日立化成工業株式会社製)、
I−819(商品名、ビスアシルフォスフィンオキサイド、チバスペシャリティーケミカルズ株式会社製)、
I−OXE−01(商品名、フェニルチオベンゾイルオキシム、チバスペシャリティーケミカルズ株式会社製)、
A−NPG(商品名、ネオペンチルグリコールジアクリレート、新中村化学工業株式会社製)、
FA−321M(商品名、エトキシ変性ビスフェノールAジメタクリレート、日立化成工業株式会社製)、
UN−904(商品名、エチレン性不飽和基数が10である光重合性化合物(10官能アクリレート)、根上工業社製)、
UN−905(商品名、エチレン性不飽和基数が15である光重合性化合物(15官能アクリレート)、根上工業社製)。
実施例及び比較例の感光性樹脂組成物の溶液を、シリコン基板上にスピンコーターを用いて均一に塗布し、110℃のホットプレートで5分間乾燥し、乾燥後の膜厚30μm、サイズ10mm×10mmの感光性樹脂組成物層を形成した。この感光性樹脂組成物層を形成した試験基板について、ウシオ電機社製のプロキシミティー露光機(商品名:UX−1000SM)を用いて露光量600mJ/cm2で感光性樹脂組成物層の露光を行い、光硬化させた。次いで、この感光性樹脂組成物層の硬化膜が形成されたシリコン基板を1cm角にカットして試験片を得た。この試験片を、有機溶剤系現像液であるシクロヘキサノンに浸漬し、光硬化後の感光性樹脂組成物層(レジスト)の剥離及び膨潤の有無を確認することで、下記の基準に基づいて耐溶剤性を評価した。その結果を表2に示す。なお、耐溶剤性の評価が「C」のものは、溶剤現像が困難なため、他の評価を行わなかった。
A:3分経過後もレジストの剥離及び膨潤がない。
B:1〜3分の間にレジストが剥離及び/又は膨潤した。
C:1分以内にレジストが剥離及び/又は膨潤した。
実施例及び比較例の感光性樹脂組成物の溶液を、シリコン基板上にスピンコーターを用いて均一に塗布し、110℃のホットプレートで5分間乾燥し、乾燥後の膜厚30μmの感光性樹脂組成物層を形成した。この感光性樹脂組成物層を形成した試験基板について、ホール径100μmφの開口パターンを有するネガマスクを介して、ウシオ電機社製のプロキシミティー露光機(商品名:UX−1000SM)を用いて露光量600mJ/cm2で感光性樹脂組成物層の露光を行った。この試験基板を、有機溶剤系現像液であるシクロヘキサノンに5分間浸漬して現像を行った。現像後のレジストパターンを観察し、下記の基準に基づいて耐溶剤性を評価した。その結果を表2に示す。
A:ホール径100μmφが開口しており、現像後残渣もない。
B:ホール径100μmφは開口しているが、現像後残渣がある。
C:ホール径100μmφが開口していない。
実施例及び比較例の感光性樹脂組成物の溶液を、シリコン基板上にスピンコーターを用いて均一に塗布し、110℃のホットプレートで5分間乾燥し、乾燥後の膜厚30μmの感光性樹脂組成物層を形成した。この感光性樹脂組成物層を形成した試験基板について、ウシオ電機社製のプロキシミティー露光機(商品名:UX−1000SM)を用いて露光量600mJ/cm2で感光性樹脂組成物層の露光を行い、光硬化させた。その後、感光性樹脂組成物層を、120℃で40分間、続いて200℃で60分間加熱して硬化させた。この試験基板を、121℃、100%RH、2気圧の条件下に100時間放置した後、硬化膜の外観を目視にて評価し、更に接着性をJIS K5400(1990年)に準拠した碁盤目試験にて評価した。評価基準は以下の通りである。その結果を表2に示す。
A:硬化膜に剥離、膨れ、クラックが見られない。
B:硬化膜に若干の剥離、膨れ、クラックの、どれか一つでも見られる。
C:硬化膜に剥離、膨れ、クラックの、どれか一つでも見られる。
テープ剥離後の残マス数が、
A:100/100(剥離無し)
B:≧90/100(1〜10マスの剥離)
C:<90/100(剥離が10マスよりも多い)
実施例及び比較例の感光性樹脂組成物の溶液を、アプリケーターを用いて、厚さ1mmのガラス板上に均一に塗布し、110℃のホットプレートで5分間乾燥し、乾燥後の膜厚30μmの感光性樹脂組成物層を形成した。この感光性樹脂組成物層を形成した試験基板について、ウシオ電機社製のプロキシミティー露光機(商品名:UX−1000SM)を用いて露光量600mJ/cm2で感光性樹脂組成物層の露光を行い、光硬化させた。その後、感光性樹脂組成物層を、120℃で40分間、続いて200℃で60分間加熱して硬化させた。この試験基板を精製水に24時間浸漬し、浸漬前後での重量変化から下記式(I)により吸水率を求め、その値から下記の基準に基づいて吸水率を評価した。その結果を表2に示す。
吸水率(%)=(浸漬後硬化膜重量−浸漬前硬化膜重量)/(浸漬前硬化膜重量)×100 (I)
A:吸水率<0.8%
B:0.8%≦吸水率≦1.2%
C:吸水率>1.2%
実施例及び比較例の感光性樹脂組成物の溶液を、アプリケーターを用いて、厚さ1mmのガラス板上に均一に塗布し、110℃のホットプレートで5分間乾燥し、乾燥後の膜厚30μmの感光性樹脂組成物層を形成した。この感光性樹脂組成物層を形成した試験基板について、ウシオ電機社製のプロキシミティー露光機(商品名:UX−1000SM)を用いて露光量600mJ/cm2で感光性樹脂組成物層の露光を行い、光硬化させた。得られた硬化膜を剥離して3mm×3mmに刻んだ試験片を作製し、TG−DTA法を用いて測定を行った。このとき、5%重量減少温度を耐熱性の値とした。その結果を表2に示す。
使用装置:Seiko Instruments Inc.TG/DTA6300
測定条件:温度範囲;25℃〜400℃、昇温速度;10℃/min、測定雰囲気;空気
Claims (8)
- (A)主鎖に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、前記炭素数に分岐部分の炭素数は含めない)を有するポリアミック酸と、
(B)重合性化合物と、
(C)光重合開始剤と、
を含有し、
前記(B)重合性化合物が、分子内に4〜10のエチレン性不飽和基を有する重合性化合物を含む、感光性樹脂組成物。 - 前記(B)重合性化合物が、更にビニル基含有エポキシ樹脂を含む、請求項1又は2記載の感光性樹脂組成物。
- 前記(A)ポリアミック酸が、下記一般式(2)で表される構造を有する化合物を含む、請求項1〜3のいずれか一項に記載の感光性樹脂組成物。
[式(2)中、Ar1は4価の有機基を示し、Ar2は2価の有機基を示し、kは1以上の整数を示す。但し、Ar1が下記一般式(3)で表される4価の有機基、及び/又は、Ar2が下記一般式(4)で表わされる2価の有機基を示す。]
[式(3)中、Xは炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、前記炭素数に分岐部分の炭素数は含めない)を示し、R1及びR2はそれぞれ独立に水素原子、炭素数1〜6のアルキル基又は炭素数1〜3のアルコキシ基を示し、m及びnはそれぞれ独立に1〜3の整数を示す。]
[式(4)中、Zは単結合又は2価の有機基を示し、Y1及びY2はそれぞれ独立に炭素数5〜20の直鎖状又は分岐状のアルキレン基(但し、分岐状の場合、前記炭素数に分岐部分の炭素数は含めない)を示す。] - 前記一般式(4)中の前記Zが、下記一般式(5)、(6)又は(7)で表される2価の有機基である、請求項1〜4のいずれか一項に記載の感光性樹脂組成物。
[式(5)中、R3は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、qは1〜4の整数を示す。なお、qが2以上の場合、複数存在するR3は同一でも異なっていてもよい。]
[式(6)中、R4は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、rは1〜4の整数を示す。なお、rが2以上の場合、複数存在するR4は同一でも異なっていてもよい。]
[式(7)中、R5は水素原子、炭素数1〜10のアルキル基、炭素数1〜10のアルケニル基又は炭素数1〜3のアルコキシ基を示し、sは1〜4の整数を示す。なお、sが2以上の場合、複数存在するR5は同一でも異なっていてもよい。] - SAWフィルタの形成に用いられる、請求項1〜5のいずれか一項に記載の感光性樹脂組成物。
- 請求項1〜6のいずれか一項に記載の感光性樹脂組成物からなる樹脂硬化物を備えるSAWフィルタ。
- 基板上に、請求項1〜6のいずれか一項に記載の感光性樹脂組成物からなる感光性樹脂組成物層を積層し、該感光性樹脂組成物層の所定部分に活性光線を照射して露光部を光硬化せしめ、次いで、前記感光性樹脂組成物層の前記露光部以外の部分を有機溶剤系の現像液を用いて除去した後、前記感光性樹脂組成物層の前記露光部を熱硬化させて樹脂硬化物を形成する工程を含む、SAWフィルタの製造方法。
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