TWI485521B - 正型感光樹脂組成物 - Google Patents
正型感光樹脂組成物 Download PDFInfo
- Publication number
- TWI485521B TWI485521B TW099121014A TW99121014A TWI485521B TW I485521 B TWI485521 B TW I485521B TW 099121014 A TW099121014 A TW 099121014A TW 99121014 A TW99121014 A TW 99121014A TW I485521 B TWI485521 B TW I485521B
- Authority
- TW
- Taiwan
- Prior art keywords
- alkali
- weight
- resin composition
- positive photosensitive
- photosensitive resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 64
- 239000004925 Acrylic resin Substances 0.000 claims description 36
- 229920000178 Acrylic resin Polymers 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 239000005011 phenolic resin Substances 0.000 claims description 26
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 claims description 21
- 239000000654 additive Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 11
- 229920001568 phenolic resin Polymers 0.000 claims description 11
- QVEIBLDXZNGPHR-UHFFFAOYSA-N naphthalene-1,4-dione;diazide Chemical compound [N-]=[N+]=[N-].[N-]=[N+]=[N-].C1=CC=C2C(=O)C=CC(=O)C2=C1 QVEIBLDXZNGPHR-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 36
- 229920002120 photoresistant polymer Polymers 0.000 description 30
- 238000007747 plating Methods 0.000 description 19
- 239000000758 substrate Substances 0.000 description 17
- -1 gallic acid ester Chemical class 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000011889 copper foil Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 101100046775 Arabidopsis thaliana TPPA gene Proteins 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
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- 238000002360 preparation method Methods 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
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- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-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
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- FDQQNNZKEJIHMS-UHFFFAOYSA-N 3,4,5-trimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1C FDQQNNZKEJIHMS-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
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-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
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- 150000001299 aldehydes Chemical class 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
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- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 229920002223 polystyrene Polymers 0.000 description 1
- ILPVOWZUBFRIAX-UHFFFAOYSA-N propyl 2-oxopropanoate Chemical compound CCCOC(=O)C(C)=O ILPVOWZUBFRIAX-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
Description
本發明係關於一種正型感光樹脂組成物,尤其是適用於半加成製程(Semi-Additive Process)之正型感光樹脂組成物。
習知印刷電路板,是利用減去製程(Subtractive Process)對基板表面的金屬層進行蝕刻,以形成配線圖案。然而,隨著電子產品微型化的發展趨勢,縮小線寬/間距以提高產品密度已成為電路板製作的一個重要方向。因此,遂發展出利用電鍍方式於基板上形成配線圖案的加成製程(Additive Process),以克服減去製程在細間距線路製作時的不穩定性。加成製程包括全加成製程(Full-Additive Process)及半加成製程(Semi-Additive Process)。全加成製程係將光阻劑塗佈於基板絕緣層上,藉由微影製程將光阻劑圖案化後作為電鍍光阻,然後,藉由無電電鍍,在暴露於電鍍光阻外的絕緣層上形成配線圖案後,蝕刻移除光阻劑。而半加成製程係於基板絕緣層上形成金屬薄層,並將光阻劑塗佈於金屬薄層上,再藉由微影製程將光阻劑圖案化後作為電鍍光阻,接著藉由電解電鍍,在暴露於電鍍光阻外的金屬薄層上形成配線圖案後,蝕刻移除光阻劑及其下方的金屬薄層。台灣專利第I312649號揭示有應用半加成製程製作印刷電路板的方法。
目前,電路板業界普遍採用半加成製程,並使用負型光阻劑來製作電路板的配線圖案。負型光阻劑經光線照射後會產生交聯(cross link),而難溶於顯影液,因此,在微影製程中,負型光阻劑被光罩遮蔽的部份(未曝光的部分),會溶解於顯影液而除去。台灣專利第200906259號揭露將負型光阻劑應用於半加成製程,以製作具有間距小於40μm(線寬/間距=20/20μm)的線路。負型光阻劑包括乾膜光阻劑以及液態光阻劑。乾膜光阻劑係以薄膜的形式貼附於基板,因此,使用便利且具經濟效益,然其對基板的附著性較差,解析度也較差。液態光阻劑則以溶液的形式塗敷於基板上,並乾燥形成薄膜,其可對基板上的絕緣層或金屬薄層表面提供高附著性,並具有較高的解析度。台灣專利第I226089號揭示乾膜光阻劑於半加成製程的應用;台灣專利第200704297號揭露液態負型光阻劑於半加成製程的應用;而台灣專利第200501852號則揭露同時使用液態及薄膜之負型光阻劑,並藉由半加成製程,以形成線寬/間距=15/15μm的線路(參見實施例1及2)。
惟,習知的光阻劑容易裂化或是對基板上的絕緣層或金屬薄層的附著能力不夠良好,因此,容易導致電鍍材料滲透至電鍍光阻下方(滲鍍)或者導致電鍍光阻剝落,從而造成配線圖案的形成失敗。再者,因為習知的光阻劑具有較差的對比性(contrast)或是對電鍍液具有較差的耐侵蝕性,因而易產生不良的線路形狀。此外,當欲製作具高解析度的線路(例如:線距<12μm)時,習知的負型光阻劑由於技術上的限制,並不能滿足此等需求;或者需轉用昂貴的設備,才能利用習知的負型光阻劑製作具高解析度的線路。
因此,亟需具有良好附著能力及耐電鍍能力,且能用於半加成製程以製作更精細線路的光阻劑,以滿足產業的需求。
鑒於上述習知技術之缺點,本發明提供一種正型感光樹脂組成物,包括:(A)鹼可溶性酚醛樹脂,其重量平均分子量為8000至30000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性酚醛樹脂的含量為20至40 wt%;(B)鹼可溶性丙烯酸系樹脂,其重量平均分子量為5000至55000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性丙烯酸系樹脂的含量為5至20 wt%;(C)含有醌二疊氮基感光化合物,且以該正型感光樹脂組成物的總重為基準,該含有醌二疊氮基感光化合物的含量為1至15 wt%;以及(D)其餘的溶劑。
根據本發明一具體實施例,鹼可溶性丙烯酸系樹脂包含如下式(I)、(II)及(III)所示之單元:
(C)含有醌二疊氮基感光化合物係由萘醌二疊氮磺酸化物與選自於下式(C-1)、(C-2)、(C-3)或(C-4)化合物所形成者,
根據本發明,以正型感光樹脂組成物的總重為基準,含有醌二疊氮基感光化合物的含量為1至30 wt%,較佳為1至20 wt%,最佳為1至15 wt%。
本發明之正型感光樹脂組成物,藉由鹼可溶性酚醛樹脂、鹼可溶性丙烯酸系樹脂及含有醌二疊氮基之化合物之組合,特別適用於半加成製程,該正型感光樹脂組成物用於半加成製程時可製作更精細之線路,且具有良好附著能力及耐電鍍能力。
以下係藉由特定的具體實施例說明本發明之實施方式,熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。本發明也可藉由其他不同的具體實施例加以施行或應用,本說明書中的各項細節亦可基於不同觀點與應用,在不悖離本創作之精神下進行各種修飾與變更。
本發明之適用於半加成製程(Semi-Additive Process)之正型感光樹脂組成物係包括:
(A) 鹼可溶性酚醛樹脂;
(B) 鹼可溶性丙烯酸系樹脂;
(C) 含有醌二疊氮基感光化合物;以及
(D) 溶劑。
用於本發明之正型感光樹脂組成物(A)鹼可溶性酚醛樹脂的重量平均分子量為8000至30000。
本文所使用之「重量平均分子量」,係利用凝膠滲透層析(GPC)測量四氫呋喃(THF)溶劑中樣品相對於聚苯乙烯標準品之測量值。
正型感光樹脂組成物中,(A)鹼可溶性酚醛樹脂的含量,以正型感光樹脂組成物的總重為基準,為20至40 wt%,較佳為25至35 wt%。
鹼可溶性酚醛樹脂可以習知方法由,例如,使用具有酚系羥基之芳香族化合物(以下,簡稱「酚類」)和醛類進行加成縮合反應而製得。上述鹼可溶性酚醛樹脂的製備方法為本領域具有通常知識者所熟知,故不再贅述。
酚類的實例包括(但不限於)苯酚、鄰甲酚、間甲酚、對甲酚、鄰乙基苯酚、間乙基苯酚、對乙基苯酚、鄰丁基苯酚、間丁基苯酚、對丁基苯酚、2,3-二甲苯酚、2,4-二甲苯酚、2,5-二甲苯酚、2,6-二甲苯酚、3,4-二甲苯酚、3,5-二甲苯酚、2,3,5-三甲基苯酚、3,4,5-三甲基苯酚、對苯基苯酚、間苯二酚、氫醌、氫醌-甲基醚、焦棓酚(pyrogallol)、間苯三酚(phloroglucinol)、羥基聯苯、雙酚A、五倍子酸、五倍子酸酯、α-萘酚及β-萘酚等。醛類的實例包括(但不限於)甲醛、多聚甲醛、糠醛、苯甲醛、硝基苯甲醛及乙醛等。
於一具體實施例中,用於本發明之正型感光樹脂組成物的(A)鹼可溶性酚醛樹脂中苯基重複單元上之該甲基可與羥基係可形成間位關係(meta)或對位關係(para),且該鹼可溶性酚醛樹脂(A)可由兩種以上的酚醛樹脂混合而得,例如,可由第一酚醛樹脂與第二酚醛樹脂組成本發明之鹼可溶性酚醛樹脂(A)。
本文所使用之術語「丙烯酸系樹脂」包含丙烯酸系樹脂及甲基丙烯酸系樹脂。本文所使用之術語「(甲基)丙烯酸」包含丙烯酸及甲基丙烯酸。
用於本發明之正型感光樹脂組成物的(B)鹼可溶性丙烯酸系樹脂其重量平均分子量為5000至55000,較佳為10000至25000。根據本發明一具體實施例,用於正型感光樹脂組成物之鹼可溶性丙烯酸系樹脂(B)的重量平均分子量為20000至35000。
正型感光樹脂組成物中,以正型感光樹脂組成物的總重為基準,(B)鹼可溶性丙烯酸系樹脂的含量為5至20 wt%,較佳為10至20 wt%,當(B)鹼可溶性丙烯酸系樹脂小於5重量份時,將造成組成物耐電鍍能力較差,易有滲鍍與脆裂現象產生;反之,大於30重量份時,會造成組合物對比(contrast)下降,使得組成物顯影後線路圖像不佳。
用於本發明之正型感光樹脂組成物的(B)鹼可溶性丙烯酸系樹脂,較佳為包含以乙烯系不飽和酸為必要單體進行單獨聚合或共聚合而得之丙烯酸系樹脂,更佳為包含乙烯系不飽和酸與含有乙烯系不飽和鍵之單體的共聚物。
乙烯系不飽和酸的實例包括(但不限於)(甲基)丙烯酸、丁烯酸(crotonic acid)、順丁烯二酸、反丁烯二酸、甲基順丁烯二酸(citroconic acid)、甲基反丁烯二酸、伊康酸(itaconic acid)、己二烯酸及其組合等。於本發明一具體實施例中,乙烯系不飽和酸為(甲基)丙烯酸。根據本發明一具體實施例,(B)鹼可溶性丙烯酸系樹脂係含有至少一種乙烯系不飽和酸。
含有乙烯系不飽和鍵之單體的實例包括(但不限於)經取代或未經取代之(甲基)丙烯酸C1~C18烷基酯;較佳為經取代或未經取代之(甲基)丙烯酸C1~C8烷基酯。根據本發明一具體實施例,(B)鹼可溶性丙烯酸系樹脂可使用一種以上的含有乙烯系不飽和鍵之單體。
根據本發明一具體實施例,用於本發明之正型感光樹脂組成物的(B)鹼可溶性丙烯酸系樹脂包含如下式(I)、(II)及(III)所示之單元:
於一具體實施例中,(B)鹼可溶性丙烯酸系樹脂中,式(I)之單元佔該鹼可溶性丙烯酸系樹脂較佳的為5至50%重量比,更佳的為10至30%重量比,當比例未滿5%重量比,則所得組成物對於鹼性顯像液的溶解性有降低之傾向,另一方向,若超過50重量%,則對於鹼性顯像液的溶解性過大,以鹼性顯像液予以顯像時,光阻圖案易由基板上脫落並且具有易造成圖案表面膜破壞之傾向;式(II)之單元佔該鹼可溶性丙烯酸系樹脂較佳的為40至90%重量比,更佳的為50至80%重量比,當比例未滿40%重量比,將造成組成物耐電鍍能力較差,易有滲鍍與脆裂現象產生,另一方向,若超過80重量%,則所得組成物對於鹼性顯像液的溶解性有降低之傾向;以及式(III)之單元佔該鹼可溶性丙烯酸系樹脂較佳的為5至30%重量比,更佳的為10至20%重量比,當比例未滿5%重量比,將造成組成物耐電鍍能力較差,易有滲鍍與脆裂現象產生,另一方向,若超過20重量%,則所得組成物對於鹼性顯像液的溶解性有降低之傾向。
用於本發明之正型感光樹脂組成物的含有(C)醌二疊氮基感光化合物,係為萘醌二疊氮磺酸化物與具有1個以上之苯酚性氫氧基化合物反應,例如,1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸與苯酚性氫氧基化合物之完全酯化合物,部份酯化化合物者。
本發明組成物中,(C)含有醌二疊氮基感光化合物,可單獨一種使用,亦可含有2種以上混合使用。
較佳的含有醌二疊氮基感光化合物(C)為1,2-萘醌二疊氮磺酸與具有羥基之多元酚反應而得之酯化物,例如,1,2-萘醌二疊氮磺酸與2,3,4-三羥二苯基酮、雙(4-羥基-2,5-二甲基苯)-3,4-二羥苯甲烷、1,1,1-三(4-羥基苯基)乙烷、4,4’-[1-[4[1-(4-羥苯基)-1-甲基乙基]苯基]亞乙基]雙酚、或2,3,4,4’-四羥二苯基甲烷反應而得之酯化物。根據本發明一具體實施例,可使用至少一種含有醌二疊氮基之化合物。
根據本發明一具體實施例,用於正型感光樹脂組成物的(C)含有醌二疊氮基感光化合物含如1,2-萘醌二疊氮-4-磺酸、1,2-萘醌二疊氮-5-磺酸等與下式(C-1)、(C-2)、(C-3)或(C-4)化合物形成磺酸酯化物
正型感光樹脂組成物中,以正型感光樹脂組成物的總重為基準(C)含有醌二疊氮基感光化合物的含量為1至30 wt%,較佳為1至20 wt%,最佳為1至15 wt%,當(C)含有醌二疊氮基感光化合物小於1 wt%時,會造成感光不足,使得組成物顯影後無法形成線路圖像;反之,大於30重量份時,會造成組合物對比(contrast)下降,使得組成物顯影後線路圖像不佳。
根據本發明一具體實施例,正型感光樹脂組成物通常使用溶劑以調製成液狀組成物而使用。正型感光樹脂組成物所使用之溶劑並無特別限定,只要可將正型感光樹脂組成物的成分分散或溶解,而不與這些成分起反應。
根據本發明一具體實施例,正型感光樹脂組成物中,以正型感光樹脂組成物的總重為基準,溶劑的含量為20至90 wt%,較佳為25至80wt%,更佳為25至74 wt%。
溶劑的實例包括(但不限於)醚類,例如,乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單正丁醚、二甘醇單甲醚、二甘醇單乙醚、二甘醇單正丙醚、二甘醇單正丁醚、三甘醇單甲醚、三甘醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、二丙二醇單甲醚、三丙二醇單乙醚、二甘醇二甲醚、二甘醇甲基乙醚、二甘醇二乙醚及四氫呋喃等;酮類,例如,甲基乙基酮、環己酮、2-庚酮及3-庚酮等;酯類,例如,乙二醇單甲醚醋酸酯、乙二醇單乙醚醋酸酯、二甘醇單甲醚醋酸酯、二甘醇單乙醚醋酸酯、丙二醇單甲醚醋酸酯、丙二醇單甲醚醋酸酯(PGMEA)、2-羥基丙酸甲酸、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基醋酸乙酯、羥基醋酸乙酯、2-羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基醋酸酯、3-甲基-3-甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酸、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、甲酸正戌酸、醋酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯醋酸甲酯、乙醯醋酸乙酯及2-羥基丁酸乙酯等;芳香族類,例如,甲苯及二甲苯等;醯胺族類,例如,N-甲基吡咯烷酮、N,N-二甲基甲醯胺及N,N-二甲基乙醯胺等。根據本發明一具體實施例,可使用至少一種上述溶劑。
此外,上述溶劑亦可與芐基乙醚、二-正己醚、乙睛丙酮、異佛爾酮、己酸、庚酸、1-辛醇、1-萘醇、芐醇、醋酸芐酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙二醇單苯醚醋酸酯等高沸點溶劑併用。
根據本發明一具體實施例,正型感光樹脂組成物可視需要加入添加劑。添加劑的實例包括(但不限於)色素、染料(dyes)、溶解抑制劑(dissolution inhibitors)、界面活性劑(例如:氟系界面活性劑,fluoro-surfactant)、熱聚合物抑制劑、增稠劑、防沫劑、增感劑(sensitizers)、抗氧化劑及偶聯劑。正型感光樹脂組成物中,添加劑的含量,以正型感光樹脂組成物的總重為基準,通常不超過5 wt%。
將本發明之正型感光樹脂組成物應用於半加成製程時,可於基板上形成該正型感光樹脂組成物。
將本發明之正型感光樹脂組成物用於製作線路時,可於基板上形成該正型感光樹脂組成物,並圖案化該正型感光樹脂組成物,接著形成金屬線路。
取(A)30克酚醛樹脂(由對-甲酚100克、間-甲酚100克、37%甲醛120克以草酸觸媒進行縮合所得到的酚醛樹脂,重量平均分子量約為20,000),此共聚合物稱為鹼可溶性酚醛樹脂(a)。
以附有乾冰/甲醇回流冷凝器與溫度計之燒瓶進行氮取代後,加入起始劑2,2’-偶氮雙異丁基(AIBN)3.0克,及做為溶劑225克之2-羥基丙酸乙酯後,攪拌至聚合起始劑溶解為止。使用的單體為甲基丙烯酸20克、甲基丙烯酸甲酯70克、2-乙基丙烯酸己酯10克進行聚合反應,緩緩進行攪拌。隨後,並升溫至約80℃,於此溫度下進行聚合4小時。再冷卻至室溫後,燒瓶內以空氣取代,之後再加入150毫克之對甲氧基苯酚作為穩定劑。反應生成物滴入多量甲醇後使反應物凝固之。水洗此凝固物後與凝固物同重量之四氫呋喃中進行再溶解後,以多量甲醇再度進行凝固。此再溶解-凝固之操作重覆進行3次後,將取得凝固物於40℃下進行真空乾燥48小時後,取得丙烯酸共聚合物,(重量平均分子量約30000),此共聚合物稱為丙烯酸樹脂(b)。
(C1):TPPA感光化合物
以4,4’-[1-[4[1-(4-羥苯基)-1-甲基乙基]苯基]亞乙基]雙酚(4,4’-[1-[4-[1-(4-Hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol) 1莫耳與2.0莫耳之萘酚-1,2-二疊氮-4-磺醯氯化物之酯化反應生成物,此生成物稱為TPPA感光化合物。
(C2):THPE感光化合物
以1,1,1-三(4-羥基苯基)乙烷(1,1,1-Tris(p-hydroxyphenyl)ethane) 1莫耳與2.0莫耳之萘酚-1,2-二疊氮-5-磺醯氯化物之酯化反應生成物,此生成物稱為THPE感光化合物。
(C3):MAC-4感光化合物
以2,3,4-三羥基二苯甲酮(2,3,4-Tri-hydroxy-benzophenone) 1莫耳與2.0莫耳之萘酚-1,2-二疊氮-4-磺醯氯化物之酯化反應生成物,此生成物稱為MAC-4感光化合物。
(C4):THDM感光化合物
以2,3,4,4’-四羥二苯基甲烷(2,3,4,4’-Tetrahydroxydiphenylmethane) 1莫耳與2.0莫耳之萘酚-1,2-二疊氮-5-磺醯氯化物之酯化反應生成物,此生成物稱為THDM感光化合物。
取(A) 30克鹼可溶性酚醛樹脂(a)、(B) 16克丙烯酸樹脂(b)、(C) 6克醌二疊氮基之感光化合物TPPA、及(D) 48克溶劑丙二醇單甲基醚乙酸酯(PGMEA),配成100克的感光樹脂組成物,將上述各成份混合均勻,然後以10μm的過濾器過濾此溶液,光阻劑組成物配方製備完成。
重複實施例1之步驟,使用各成分如表一的配方,來製備光阻劑組成物。
重複實施例1之步驟,使用各成分如表一的配方,來製備光阻劑組成物。
對上述實施例及比較例所得之感光樹脂組成物進行線路形狀(profile)、線路間距(pitch)、曝光能量、附著能力、耐電鍍能力等之測試。
對上述實施例及比較例所得之感光樹脂組成物,以旋轉塗佈機(spin coater)塗佈至銅箔基材上,控制旋轉塗佈機(spin coater)之轉速,使得組成物經烘箱(oven)烘烤110℃/15min後,膜厚達到9至11um。接著,將組成物取出烘箱後,於室溫下靜置1小時。再透過光罩(mask)以接觸式曝光機(廠牌:群翊型號:GPE-5K進行曝光作業。於23℃以顯影液EPD2000(2.38w%TMAH含界面活性劑)以沉浸方式(dipping)進行顯影作業。之後再進行下列測試,並將結果記錄於表一,其中,各符號之說明如下:
於上述顯影作業完成後,裁切成適當大小,以場發射電子顯微鏡SEM(廠牌:Hitachi型號:S-4200)來觀察其線路形狀;並量測其上幅(top)與下幅(bottom)寬度
◎:線路上幅除於下幅>0.83
○:線路上幅除於下幅介於0.70至0.83
△:線路上幅除於下幅介於0.60至0.69
X:線路上幅除於下幅<0.60,或是剝落(peeling)
於上述顯影作業完成後,裁切成適當大小,以掃描式電子顯微鏡SEM(廠牌:Hitachi型號:S-4200)來觀察其可顯影之線路間距。
○:線路間距可達6um以下
X:線路間距不可達6um以下,或是剝落
將組成物以旋轉塗佈機塗佈至銅箔基材上,控制旋轉塗佈機之轉速,使得組成物經烘箱烘烤110℃/15min後,膜厚達到9至11um。接著,將組成物取出烘箱後,於室溫下靜置1小時。再透過光罩以接觸式曝光機(廠牌:群翊 型號:GPE-5K進行曝光作業。而曝光能量(mj)過大,會造成產速過慢,不利於製造生產。
◎:曝光能量<190mj
○:曝光能量介於190mj至220mj
△:曝光能量介於221mj至250mj
X:曝光能量>250mj
將組成物以旋轉塗佈機塗佈至銅箔基材上,控制旋轉塗佈機之轉速,使得組成物經烘箱烘烤110℃/15min後,膜厚達到9至11um。接著,將組成物取出烘箱後,於室溫下靜置1小時。再透過光罩以接觸式曝光機(廠牌:群翊 型號:GPE-5K進行曝光作業。於23℃以顯影液EPD2000(2.38 w% TMAH含界面活性劑)以沉浸方式進行顯影作業。顯影完,進行電鍍銅、電鍍金(Au(CN)2系列)測試後,再以場發射電子顯微鏡SEM(廠牌:Hitachi型號:S-4200)來觀察組成物底部是否滲鍍而翹起。
○:無滲鍍、無翹起
X:滲鍍
將組成物以旋轉塗佈機塗佈至銅箔基材上,控制旋轉塗佈機之轉速,使得組成物經烘箱烘烤110℃/15min後,膜厚達到9至11um。接著,將組成物取出烘箱後,於室溫下靜置1小時。再透過適當光罩以接觸式曝光機進行曝光作業。於23℃以顯影液EPD2000(2.38w%TMAH含界面活性劑)以沉浸方式進行顯影作業。顯影完,進行電鍍銅、電鍍金(Au(CN)2系列)測試後,再以電子顯微鏡觀察組成物表面是否會脆裂,其中
○:無脆裂
X:脆裂
測試結果示於下表二。
由表二可知,加入本發明之丙烯酸系樹脂可改善一般酚醛樹酯過於硬脆的特性,使得組成物在電鍍時不易脆裂,且可增進對基材的附著能力。
本發明之正型感光樹脂組成物具有良好的附著能力及耐電鍍能力;再者,本發明之正型感光樹脂組成物可應用於半加成製程,以製作精細的線路;此外,應用本發明之正型感光樹脂組成製作的線路,具有良好的線路形狀,因此,本發明之正型感光樹脂組成物,實能充分符合產業利用的需求。
上述實施例僅例示性說明本發明之組成物與製備方法,而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下,對上述實施例進行修飾與改變。因此,本發明之權利保護範圍,應如後述之申請專利範圍所載。
Claims (12)
- 一種正型感光樹脂組成物,包括:(A)鹼可溶性酚醛樹脂,其重量平均分子量為8000至30000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性酚醛樹脂的含量為20至40wt%;(B)鹼可溶性丙烯酸系樹脂,其重量平均分子量為5000至55000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性丙烯酸系樹脂的含量為5至20wt%,其中,該鹼可溶性丙烯酸系樹脂包含如下式(I)、(II)及(III)所示之單元:
;(C)含有醌二疊氮基感光化合物,且以該正型感光樹脂組成物的總重為基準,該含有醌二疊氮基感光化合物的含量為1至15wt%;以及(D)其餘的溶劑。 - 如申請專利範圍第1項所述之正型感光樹脂組成物,其中,式(I)之單元佔該鹼可溶性丙烯酸系樹脂之10至 30重量%;式(II)之單元佔該鹼可溶性丙烯酸系樹脂之50至80重量%;以及式(III)之單元佔該鹼可溶性丙烯酸系樹脂之10至20重量%。
- 如申請專利範圍第1項所述之正型感光樹脂組成物,其中,該鹼可溶性酚醛樹脂的重量平均分子量為10000至25000。
- 如申請專利範圍第1項所述之正型感光樹脂組成物,其中,該鹼可溶性丙烯酸系樹脂的重量平均分子量為20000至35000。
- 如申請專利範圍第1項所述之正型感光樹脂組成物,其中,(C)含有醌二疊氮基感光化合物係由萘醌二疊氮磺酸化物與選自於下式(C-1)、(C-2)、(C-3)或(C-4)化合物所形成者
- 如申請專利範圍第5項所述之正型感光樹脂組成物,其中,該萘醌二疊氮磺酸化物係選自1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸。
- 一種適用於半加成製程之正型感光樹脂組成物,包括:(A)鹼可溶性酚醛樹脂,其重量平均分子量為8000至30000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性酚醛樹脂的含量為20至40wt%;(B)鹼可溶性丙烯酸系樹脂,其重量平均分子量為5000至55000,且以該正型感光樹脂組成物的總重為基準,該鹼可溶性丙烯酸系樹脂的含量為5至20wt%,其中,該鹼可溶性丙烯酸系樹脂包含如下式(I)、(II)及(III)所示之單元:
(C)含有醌二疊氮基感光化合物,且以該正型感光樹脂組成物的總重為基準,該含有醌二疊氮基感光化合物的含量為1至15wt%;以及(D)其餘的溶劑。 - 如申請專利範圍第7項所述之正型感光樹脂組成物,其中,式(II)之單元佔該鹼可溶性丙烯酸系樹脂之10至30重量%;式(III)之單元佔該鹼可溶性丙烯酸系樹脂之50至80重量%;以及式(IV)之單元佔該鹼可溶性丙烯酸系樹脂之10至20重量%。
- 如申請專利範圍第7項所述之正型感光樹脂組成物,其中,該鹼可溶性酚醛樹脂的重量平均分子量為10000至25000。
- 如申請專利範圍第7項所述之正型感光樹脂組成物,其中,該鹼可溶性丙烯酸系樹脂的重量平均分子量為20000至35000。
- 如申請專利範圍第7項所述之正型感光樹脂組成物,其 中,(C)含有醌二疊氮基感光化合物係由萘醌二疊氮磺酸化物與選自於下式(C-1)、(C-2)、(C-3)或(C-4)化合物所形成者
- 如申請專利範圍第11項所述之正型感光樹脂組成物,其中,該萘醌二疊氮磺酸化物係選自1,2-萘醌二疊氮-4-磺酸或1,2-萘醌二疊氮-5-磺酸。
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|---|---|---|---|---|
| KR0184870B1 (ko) * | 1990-02-20 | 1999-04-01 | 아사구라 다기오 | 감방사선성 수지 조성물 |
| DE4134526A1 (de) * | 1990-10-18 | 1992-05-14 | Toyo Gosei Kogyo Kk | Positive photoresist-zusammensetzung und mustererzeugungsverfahren unter verwendung dieser zusammensetzung |
| US5413896A (en) * | 1991-01-24 | 1995-05-09 | Japan Synthetic Rubber Co., Ltd. | I-ray sensitive positive resist composition |
| US5561194A (en) * | 1995-03-29 | 1996-10-01 | International Business Machines Corporation | Photoresist composition including polyalkylmethacrylate co-polymer of polyhydroxystyrene |
| JP3633179B2 (ja) * | 1997-01-27 | 2005-03-30 | Jsr株式会社 | ポジ型フォトレジスト組成物 |
| TW554250B (en) * | 2000-12-14 | 2003-09-21 | Clariant Int Ltd | Resist with high resolution to i ray and process for forming pattern |
| KR100584965B1 (ko) | 2003-02-24 | 2006-05-29 | 삼성전기주식회사 | 패키지 기판 및 그 제조 방법 |
| JP2006154434A (ja) * | 2004-11-30 | 2006-06-15 | Jsr Corp | 感光性樹脂組成物、感光性樹脂膜およびこれらを用いたバンプ形成方法 |
| CN100582939C (zh) * | 2005-02-05 | 2010-01-20 | 明德国际仓储贸易(上海)有限公司 | 正型光阻剂组成物及其应用 |
| KR101268424B1 (ko) * | 2005-10-31 | 2013-05-28 | 에이지이엠코리아 주식회사 | 포토레지스트 조성물 및 이를 이용한 박막 트랜지스터기판의 제조방법 |
| KR100794961B1 (ko) | 2006-07-04 | 2008-01-16 | 주식회사제4기한국 | 인쇄회로기판 제조용 psap 방법 |
| TWI342179B (en) | 2007-07-19 | 2011-05-11 | Samsung Electro Mech | Method of manufacturing build-up printed circuit board |
-
2010
- 2010-06-28 TW TW099121014A patent/TWI485521B/zh active
-
2011
- 2011-04-18 US US13/088,820 patent/US20110318686A1/en not_active Abandoned
- 2011-04-29 KR KR1020110040943A patent/KR20120001596A/ko not_active Ceased
- 2011-05-13 EP EP11166082A patent/EP2400344A1/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009125752A1 (ja) * | 2008-04-10 | 2009-10-15 | 旭化成イーマテリアルズ株式会社 | 感光性樹脂組成物及びそれを用いた感光性樹脂積層体 |
| JP2010015079A (ja) * | 2008-07-07 | 2010-01-21 | Tokyo Ohka Kogyo Co Ltd | ポジ型レジスト組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2400344A1 (en) | 2011-12-28 |
| US20110318686A1 (en) | 2011-12-29 |
| TW201200966A (en) | 2012-01-01 |
| KR20120001596A (ko) | 2012-01-04 |
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