CN108020988A - 感光性树脂组成物及含其的干膜光阻 - Google Patents
感光性树脂组成物及含其的干膜光阻 Download PDFInfo
- Publication number
- CN108020988A CN108020988A CN201611091034.1A CN201611091034A CN108020988A CN 108020988 A CN108020988 A CN 108020988A CN 201611091034 A CN201611091034 A CN 201611091034A CN 108020988 A CN108020988 A CN 108020988A
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- China
- Prior art keywords
- resin composition
- photosensitive resin
- dry film
- cycloalkyl
- hydroxy carbamate
- Prior art date
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Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 50
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- VSKFADHADUWCCL-UHFFFAOYSA-N carbamoperoxoic acid Chemical compound NC(=O)OO VSKFADHADUWCCL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- -1 C4-C12Alkyl Chemical group 0.000 claims description 40
- 229920000570 polyether Polymers 0.000 claims description 32
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 30
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 20
- 125000003342 alkenyl group Chemical group 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 230000000903 blocking effect Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 150000002081 enamines Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 241001232787 Epiphragma Species 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
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- 238000000034 method Methods 0.000 abstract description 7
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- VGEWEGHHYWGXGG-UHFFFAOYSA-N ethyl n-hydroxycarbamate Chemical compound CCOC(=O)NO VGEWEGHHYWGXGG-UHFFFAOYSA-N 0.000 abstract 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
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- 238000011161 development Methods 0.000 description 9
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- 241000736148 Styrax Species 0.000 description 8
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- 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 7
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
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- 150000002431 hydrogen Chemical group 0.000 description 5
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- 229940106691 bisphenol a Drugs 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
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- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
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- 150000002170 ethers Chemical class 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 241000270295 Serpentes Species 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
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- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- 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
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- 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
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- H—ELECTRICITY
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- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
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Abstract
本发明提供一种感光性树脂组成物,包含(a)不饱和单羧酸、(b)羟基氨基甲酸酯及(c)光起始剂;其可作为光阻涂料用于干膜光阻,以制造印刷电路板等电子元件。其中,该(b)羟基氨基甲酸酯具有[CC]/[NH2]为0.5至0.9特性,可提升该感光性树脂组成物用于光阻干膜的解析度、密着性,以及剥膜能力,以改善干膜光阻用在制造印刷电路及其他电子元件的制程效率和品质。
Description
技术领域
本发明关于一种感光性树脂组成物,其可作为光阻涂料,用于干膜光阻的感光阻剂层。
背景技术
干膜光阻可用于制备印刷电路板、引线框、电浆显示板或其他显示器的ITO电极或黑色矩阵等。比起湿膜光阻,干膜光阻具有制程时间快速、表面均匀性佳,以及膜厚薄等优点,且较利于使用在有孔的电路板。干膜光阻制备方法是将干膜光阻剂涂布到载体薄膜之上,待涂布层干燥后,再以另一层薄膜,例如聚乙烯薄膜,覆盖在该涂布层上,而形成光阻干膜。
将干膜光阻用于制造印刷电路板时,会经过刷膜、压膜、曝光、显影、蚀刻,以及剥膜等步骤。惟,干膜光阻的特性会影响到曝光及显影的效果,一般而言,当干膜光阻的厚度越薄时,解析度及蚀刻均匀性愈佳;而干膜光阻的表面若太过粗糙时,则共形性(conformability)会降低,造成与其他基板之间的密着性不佳。
在现今电子用品发展越来越精致化的时代,体积小的印刷电路板上,其电路的复杂度也随着提高。因此,如何能有效地将干膜光阻密着在基板,且快速剥膜无残留,以及在蚀刻时具有良好的解析度,将对其图像再现性及解析度有很大的影响。
本发明人发现,现今虽已有使用氨基甲酸乙酯(甲基)丙烯酸酯化合物的组成物、或含有含羧基的氨基甲酸乙酯(甲基)丙烯酸酯化合物的组成物作为干膜光阻的感光性树脂组成物。然而,使用该感光性树脂组成物作为干膜光阻时,于剥膜步骤会产生出残留干膜的问题,例如有孔洞的基板,其孔洞周围会有未剥离的干膜毛边,因此剥膜的速度必须得放慢,而降低了制程效率,又因为干膜的残存,进而影响显影时的解析度。亦即,氨基甲酸酯类感光性树脂组成物的干膜光阻,往往会有剥膜,以及解析度不佳的问题。
发明内容
鉴于上述的问题,本发明提供一种感光性树脂组成物,其具有高解析度、高密着性及良好的剥离能力,在作为干膜光阻时,不会影响到制程速度,并提升其制造良率,可有效应用在印刷电路板等各种电子产品领域。
即,本发明为一种感光性树脂组成物,包含(a)不饱和单羧酸、(b)羟基氨基甲酸酯及(c)光起始剂。
于较佳实施例中,该(b)羟基氨基甲酸酯为含不饱和双键羟基氨基甲酸酯聚醚化合物,并具有如下式(I):
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
R4为C4-C12的烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
于较佳实施例中,该(b)羟基氨基甲酸酯具有[CC]/[NH2]介于0.5~0.9。
于较佳实施例中,该(b)羟基氨基甲酸酯具有[CC]/[NH2]介于0.5~0.75。
于较佳实施例中,该(b)羟基氨基甲酸酯具有[EPOXY]/[AHEW]介于0.35~1。
于较佳实施例中,该感光性树脂组成物进一步包含一溶剂。
于较佳实施例中,该溶剂为一或多种选自由醇类、醚类及酮类所组成的群组。
于较佳实施例中,相对于100质量分该(a)不饱和单羧酸,该(b)羟基氨基甲酸酯为5~50质量分。
于较佳实施例中,该感光性树脂组成物用于作为光阻涂料。
本发明的另一目的在于提供一种干膜光阻,包含盖膜层、如上述任一项的感光性树脂组成物所形成的感光阻剂层,以及隔膜层。
本发明的另一目的在于提供一种羟基氨基甲酸酯聚醚化合物,具有如下式(I)的结构:
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
R4为C4-C12的烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
具体实施方式
本发明提供一种感光性树脂组成物,包含(a)不饱和单羧酸、(b)羟基氨基甲酸酯及(c)光起始剂。
上述的(a)不饱和单羧酸包含分子结构中具有烯基不饱和键及羧基的不饱和单羧酸化合物,例如(甲基)丙烯酸、丁烯酸、4-戊烯酸、5-己烯酸、己二烯酸、6-庚烯酸、α-溴(甲基)丙烯酸、α-溴(甲基)丙烯酸、β-呋喃(甲基)丙烯酸、β-苯乙烯(甲基)丙烯酸、马来酸、富马酸、肉桂酸、α-氰基-肉桂酸、衣康酸、巴豆酸等,其中较佳的实施例为(甲基)丙烯酸。
上述的(b)羟基氨基甲酸酯为含不饱和双键羟基氨基甲酸酯化合物,并具有如下式(I):
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
(IV);R4为C4-C12的烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
上述R4及R2的C4-C12烷基包含直链或支链烷基,例如正丁基、异丁基、叔丁基、戊基、异戊基等。
上述R4的烯基包含有取代或无取代的烯基,例如乙烯基、1-丙烯基、2-丙烯基或具有取代基的烯基,例如1-甲基乙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、2-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-2-丙烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-甲基-1-丁烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、1-甲基-2-丁烯基、2-甲基-2-丁烯基、3-甲基-2-丁烯基、1-甲基-3-丁烯基、2-甲基-3-丁烯基、3-甲基-3-丁烯基、1,1-二甲基-2-丙烯基、1,2-二甲基丙烯基、1-乙基-1-丙烯基、1-乙基-2-丙烯基,1-己烯基、2-己烯基、3-己烯基、4-己烯基、5-己烯基等。
上述R4的炔基包含有取代或无取代的炔基,例如乙炔基,1-丙炔基、2-丙炔基、1-丁炔基、3-丁炔基、1-甲基-2-丙炔基、1-戊炔基、2-戊炔基、3-戊炔基、1-甲基-2-丁炔基、1-甲基-3-丁炔基、2-甲基-3-丁炔基、3-甲基-1-丁炔基、1,1-二甲基-2-丙炔基、1-乙基-2-丙炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基或5-己炔基等。
上述R4及R2的环烷基包含有取代或无取代的环烷基,包含环戊基、环己基、环庚基或环辛基等。
上述R2的芳香基包含有取代或无取代的芳香基,例如苯基、1-萘基、2-萘基或具有取代基的芳香基,例如2-甲基苯基、3-甲基苯基、4-甲基苯基、2-乙基苯基、3-乙基苯基、4-乙基苯基、芐基、1-苯基乙基、2-苯基乙基、3-苯基丙基、1-苯基丁基、2-苯基丁基、3-苯基丁基或4-苯基丁基等。
上述R2的烯胺基可为但不限于二乙基三胺(diethylenetriamine)基团。
上述R4及R2的聚醚基团可为-O-(R6-O)m-R7-、-R7-O-(R6-O)m-或-R7-O-(R6-O)m-R7-的聚醚基,其中,R6及R7为相同或不同直链或支链的、饱和或不饱和的、有取代或无取代的脂族二价烃基,m为1以上,具体实例如选自由环氧乙烷、环氧丙烷及环氧丁烷所形成的聚醚基团。
上述的R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团,(甲基)丙烯酸酯基的含不饱和双键基团包含有取代或无取代的C1-C20的(甲基)丙烯酸烷酯基、(甲基)丙烯酸芳酯基等,任何具有(甲基)丙烯酸酯基的含不饱和双键基团。
上述的(b)羟基氨基甲酸酯具有[CC]/[NH2]介于0.5~0.9及/或[EPOXY]/[AHEW]介于0.125~1的特性;其中,[CC]/[NH2]以0.5~0.75为较佳,例如0.50、0.53、0.55、0.58、0.60、0.63、0.65、0.66、0.68、0.70、0.73、0.75、0.78、0.80、0.83、0.85、0.88、及0.9;[EPOXY]/[AHEW]可为0.125、0.15、0.20、0.25、0.30、0.35、0.40、0.45、0.50、0.55、0.60、0.65、0.70、0.75、0.80、0.85、0.90、0.95及1.0。当羟基氨基甲酸酯的[CC]/[NH2]介于0.5~0.9时,可提升干膜光阻的感光性树脂组成物的解析度、密着性,以及剥膜能力。
相对于100质量分上述的(a)不饱和单羧酸,上述的(b)羟基氨基甲酸酯为5至50质量分,例如5质量分、10质量分、15质量分、20质量分、25质量分、30质量分、35质量分、40质量分、45质量分、50质量分。
上述的(c)光起始剂包含2,2’,-双(2-氯苯基)-4,4’,5,5’,-四苯基-l,2'-二咪唑、2-乙基蒽酮、2-异丙基硫杂蒽酮、2-特丁基蒽酮、4-异丙基硫杂蒽酮1-羟基环已基苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉丙烷-1-酮、2-苯甲基-2-二甲胺基-1-[4-吗啉苯基]丁烷-1-酮、2-羟基-2-甲基-1-苯基丙烷-1-酮、2,4,6-三甲基苯酰基二苯基磷化氢氧化物、1-[4(2-羟基甲氧基)苯基]-2-羟基-2-甲基丙烷-1-酮、2,4-二乙基噻吨酮、2-氯噻吨酮、2,4-二甲基噻吨酮、3,3-二甲基-4-甲氧基苯甲基苯酮、苯甲基苯酮、1-氯-4-丙氧基噻吨酮、1-(4-异丙基苯基)2-己氧基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羟基-2-甲基丙烷-1-酮、4-苯酰基-4’-甲基二甲基硫化物、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基苯甲酸2-乙基己酯、4-二甲基胺基苯甲酸2-异戊酯、2,2-二乙氧基苯乙酮、苯甲酮二甲基乙缩醛、苯甲酮β-甲氧基二乙基乙缩酸、1-苯基-1,2-丙基二肟-O,O’-(2-羰基)乙氧基醚、O-苯酰苯甲酸甲酯、二[4-二甲基胺基苯基]酮、二苯甲酮、4,4’-二(二甲基胺基)二苯甲酮、4,4’-二氯二苯甲酮、苯甲基、安息香、苯甲氧基安息香、苯乙氧基安息香、异丙氧基安息香、异丁氧基安息香、新-丁氧基安息香、安息香甲基醚、安息香乙基醚、安息香异丙基醚、苄、对-二甲基胺基苯乙酮、对-新-丁基三氯苯乙酮、对-新丁基二氯苯乙酮、噻吨酮、2-甲基噻吨酮、2-异丙基甲基噻吨酮、二苯并环庚酮、α,α-二氯-4-苯氧基苯乙酮、以及4-二甲基胺基苯甲酸戊酯、2,4,5-三芳基咪唑二聚体或其衍生物、Lobine二聚物、或染料,例如无色三苯甲烷、三芳基甲烷无色染料、含染料和Lobine二聚物的复合物,且以2-异丙基硫杂蒽酮及2,2’,-双(2-氯苯基)-4,4’,5,5’,-四苯基-l,2'-二咪唑为较佳。
上述的感光性树脂组成物,其进一步包含一溶剂。其中,该溶剂为一或多种选自醇类、醚类、及酮类所组成的群组;该醇类包含单乙二醇二甲醚、二甘醇二甲醚(Diglyme)、三甘醇二甲醚(triglyme)等的乙二醇二甲醚(glyme)类;该醚类包含丙二醇单甲醚、丙二醇单乙醚、丙二醇单丁醚、丙二醇单异丁醚、丙二醇单第三丁醚等的丙二醇单烷醚类;该酮类包含丙酮、甲基乙酮等的酮类。而该等溶剂中,较佳为丙二醇甲醚或甲基乙酮。而溶剂的添加量较佳是占该感光性树脂组成物总量的1~20wt%,较佳为2~10wt%,更佳为2~7wt%,例如1wt%、2wt%、5wt%、7wt%、10wt%、12wt%、15wt%、17wt%、及20wt%。
本发明的感光性树脂组成物,可作为干膜光阻的光阻涂料。该光阻涂料用以制备干膜光阻的感光阻剂层时,是利用均匀涂布及干燥所制备而成。涂布的方法包含逆转辊式涂布机、刮板涂布机、唇口涂布机、棒式涂布机、挤压涂布机、逗点形状刮刀涂布机、转送辊涂布机、照相凹版式涂布机、喷涂机等惯用的涂布方法,以均匀厚度的涂布。干燥的方法包含IR炉、加热板、热风对流式干燥炉、对流烘箱等惯用的干燥方法,通常以50~130℃的温度干燥1~30分钟可得到膜。感光阻剂层的涂布膜厚并没有特别的限制,但一般而言干燥后的膜厚为10~300μm,较佳为12~240μm的范围适当选择,例如10μm、12μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm、75μm、80μm、85μm、90μm、95μm、100μm、105μm、110μm、115μm、120μm、125μm、130μm、135μm、140μm、145μm、150μm、155μm、160μm、165μm、170μm、175μm、180μm、185μm、190μm、195μm、200μm、205μm、210μm、215μm、220μm、225μm、230μm、235μm、240μm、245μm、250μm、255μm、260μm、265μm、270μm、275μm、280μm、285μm、290μm、295μm、300μm等。
本发明的干膜光阻,包含盖膜层、上述的感光性树脂组成物所形成的感光阻剂层,以及隔膜层。当干膜光阻用于制备印刷电路板等电子元件时,会利用压膜机的卷轮将干膜光阻底部的隔膜层撕开,使中间感光阻剂层藉由110±10℃温度的压膜滚轮将其压在加热的铜层合板面上,而干膜在压膜滚轮高温加热下,该感光阻剂层会形成流体状,使其能贴附在具有均匀粗化面的铜面上。其中,该盖膜层可为聚酯材质,如聚对苯二甲酸乙二醇酯等,具有保护感光阻剂层、隔绝氧气,以及防止或抑制光聚合作用;该隔膜层可为聚乙烯材质,具有隔绝感光性阻剂层黏着其他层的功用。
本发明的干膜光阻用于制备印刷电路板等电子元件时,会经过压膜、曝光、显影等过程。制备过程为在压膜前会先将铜层合板的表面使用研磨机研磨,水洗后在流动空气下干燥;将铜层合板以80℃加热后,该干膜光阻以高温及施压将该干膜光阻压膜于铜层合板上,并冷却至室温完成;随后,对该压膜后的干膜光阻进行曝光显影而完成。其中,该铜层合板可为单面或双面贴铜层合板;若为单面贴铜层合板时,其一面为铜箔而另一面为玻璃纤维强化环氧树脂层;若为双面贴铜层合板时,则将玻璃纤维强化环氧树脂层夹层于二铜箔之间。
本发明的另一目的在于提供一种羟基氨基甲酸酯聚醚化合物,其含不饱和双键羟基氨基甲酸酯化合物,并具有如下式(I)的结构:
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
R4为C4-C12的烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
上述的羟基氨基甲酸酯,其R1至R5的进一步技术特征同上R1至R5所述的进一步技术特征。
实施例
本发明将参照以下实施例说明,但不局限本发明的范畴于以下的实施例中。
制备例使用原料
·1,4-丁二醇的缩水甘油醚,BDGE125:长春人造树脂所生产的1,4-丁二醇的缩水甘油醚,其环氧当量介于125至130g/eq。
·双酚A的聚缩水甘油醚,BE180:长春人造树脂厂所生产的双酚A的聚缩水甘油醚,其环氧当量介于170至180g/eq。
·聚醚胺,Jeffamine D230:Huntsman公司所生产的聚醚胺。
·甲基丙烯酸缩水甘油酯(GMA):Sartomer公司提供。
·对苯二酚单甲醚(MEHQ):Borregaard公司提供。
·丁酮
制备例
制备例1-1:BE180环碳酸酯合成
将100g BE180环氧树脂、0.1~5%的四级铵盐放入反应釜中,搅拌升温至150℃,通入CO2,并于压力5kg/cm2下反应4hr,即可获得BE180环碳酸酯。计算CO2消耗量可得其转化率为93%。
制备例1-2:BDGE环碳酸酯合成
将100g BDGE125环氧树脂、0.1~5%的四级铵盐放入反应釜中,搅拌升温至150℃,通入CO2,并于压力5kg/cm2下反应4hr,即可获得BDGE环碳酸酯。计算CO2消耗量可得其转化率为93%。
制备例2:S01至S05羟基氨基甲酸酯聚醚化合物合成
将制备例1-1的BE180环碳酸酯与制备例1-2的BDGE环碳酸酯,各别与JeffamineD230聚醚胺在160℃下反应7小时,降温至80℃加入作为溶剂的丁酮,调配成固形份70%的羟基氨基甲酸酯聚醚化合物,试验配方如下表1所示。
表1
*[CC]:环碳酸酯摩尔数;[NH2]:胺摩尔数
实施例1:S06至S13含不饱和双键的羟基氨基甲酸酯聚醚化合物合成
将制备例2的S01至S05合成的羟基氨基甲酸酯于65℃与甲基丙烯酸缩水甘油酯(GMA)、对苯二酚单甲醚(MEHQ),进行反应4小时,即可获得含不饱和双键的羟基氨基甲酸酯聚醚化合物S06至S13,其等具有对应本案的式(I)化合物,其中,羟基氨基甲酸酯聚醚化合物S06至S12对应本案式(I)化合物,其R1为衍生自双酚A结构为如以下式(1)至(3)结构,R2为以下式(4)结构,R3-1及R3-4为以下式(5)及(6)结构的形式,R3-2及R3-3为氢:
将R1中的R4代入(V),(V)中R5代入则可得R1结构如下式(1)至(3)结构
R2:
R3-1及R3-4:
其中,羟基氨基甲酸酯聚醚化合物S13对应本案的式(I)化合物如下所示,其R1为如以下式(7)至(9)结构,R2为以下式(4)结构,R3-1及R3-4为以下式(5)及(6)结构的形式,R3-2及R3-3为氢:
将R4=C4代入R1中的式(II)~(IV):
R2:
R3-1及R3-4:
试验配方如表2所示,GMA为提供不饱和双键,MEHQ作为抑制剂,防止不饱和双键发生反应。
表2
注:[EPOXY]为环氧基当量。
[AHEW]为胺氢当量(amine hydrogen equivalent weight)。
实施例2:S14至S21与比较例S22-干膜光阻制备及特性测试
I、干膜光阻的制备
如以下表3所示的配方,调制感光性树脂组成物S14至S21,并将该溶液均匀涂布于16μm厚的聚对苯二甲酸乙二醇酯薄膜的盖膜层上,然后将已涂布的溶液(涂膜),使用热风对流式干燥器以75℃干燥3.5分钟,即在作为支撑体的聚对苯二甲酸乙二醇酯薄膜的单面上,得到设置了含有感光性树脂组成物的感光阻剂层的干膜光阻S14至S22,形成一感光性元件;其中,感光阻剂层的膜厚为40μm。
II、光致抗蚀图形的形成
首先,在玻璃纤维强化环氧树脂层的两面上层合铜箔(厚度35μm)形成双面贴铜层合板,在该铜层合板的铜表面,使用装上相当于网目数#600刷子的研磨机研磨,水洗后以空气流通使其干燥。接着,一边将双面贴铜层合板以80℃加温,一边将上述具干膜光阻S14至S22的感光性元件,以感光阻剂层侧密合于铜箔表面来贴合,一边以105℃加热,一边以2.5kg/cm2加压。然后,冷却至23℃,而得到双面贴铜层合板的两面上设置了感光阻剂层的层合板。
接着,在该层合板最外层的聚对苯二甲酸乙二醇酯薄膜表面上,依序层合Stouffer 21段曝格表(Stouffer 21steps sensitivity guide)以及具有作为解析性(CCPR-Pattern 5,L/S=1/1,一字型线路5-150μm)及密着性(CCP A-Pattern 5,L/S=1/3,一字型线路5-150μm)评估用底片。在此状态下,使用以5kW高压水银灯作为光源的曝光机,以Stouffer 21段曝格表的残留阶梯格数成为7格的曝光量作为感光度。
接着,去除聚对苯二甲酸乙二醇酯,将经曝光的感光阻剂层,通过用1.0wt%碳酸钠水溶液以30℃,显影喷压1.2kg/cm2以及显像点(由设备透明外罩看到已经完全显现出图样的该点距离称之)50%的显影条件去除未曝光部分后,进行显影处理,可干净地去除未曝光部分。将线未产生蛇行、缺口所生成线宽之间的间隔宽的最小值作为解析度;此外,可干净地去除未曝光部分,而且将线未产生蛇行、缺口所生成的线宽最小值作为密着度;可干净地去除未曝光部分,而且未产生缺口所生成的圆点形状最小值作为点状密着。该解析度、密着度、剥膜时间、点状密着及上述感光度的值,均越小为最佳值,实施例与比较例所测得的上数数值一并列于下表3。
表3
注:BPE500:乙氧双酚A甲基丙烯酸双酯
BCIM:2,2’-双(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-联咪唑
ITX:2-异丙基硫杂蒽酮
AMG:隐色孔雀绿
PM:丙二醇甲醚
实施例S14至S21与比较例S22的差异在于比较例S22没有添加本发明的羟基氨基甲酸酯,而实施例S14至S21相对于比较例S22,具有显像点出现时间较短、第2次显影的点状密着较小,以及剥膜时间较快等优势,显示添加本发明的羟基氨基甲酸酯能提升干膜光阻的解析、密着、以及剥膜能力。此结果也显示,当干膜光阻的感光阻剂层的感光性树脂组成物具有[CC]/[NH2]为0.5至0.9的羟基氨基甲酸酯、[EPOXY]/[AHEW]=0.35~1时,可提升干膜光阻的解析、密着、以及剥膜能力。
是以,本发明的感光性树脂组成物相较于一般感光性树脂具有提升干膜光阻的解析、密着,以及剥膜能力,适用于制造印刷电路板等电子元件。
本发明以藉上述较佳具体例进行更详述说明,惟本发明并不限定于上述所举例的实施态样,凡在本发明所揭示的技术思想范围内,对于该方法的变化或修饰,该等变化及修饰仍属本发明的范围。
Claims (11)
1.一种感光性树脂组成物,包含(a)不饱和单羧酸、(b)羟基氨基甲酸酯及(c)光起始剂。
2.如权利要求1的感光性树脂组成物,其特征在于,该(b)羟基氨基甲酸酯为含不饱和双键的羟基氨基甲酸酯聚醚化合物,并具有如下式(I):
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
R4为C4-C12烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
3.如权利要求1或2的感光性树脂组成物,其特征在于,该(b)羟基氨基甲酸酯具有[CC]/[NH2]介于0.5~0.9。
4.如权利要求3的感光性树脂组成物,其特征在于,该(b)羟基氨基甲酸酯具有[CC]/[NH2]介于0.5~0.75。
5.如权利要求1或2的感光性树脂组成物,其特征在于,该(b)羟基氨基甲酸酯具有[EPOXY]/[AHEW]介于0.125~1。
6.如权利要求1或2的感光性树脂组成物,其特征在于,进一步包含一溶剂。
7.如权利要求6的感光性树脂组成物,其特征在于,该溶剂为一或多种选自由醇类、醚类及酮类所组成的群组。
8.如权利要求1或2的感光性树脂组成物,其特征在于,相对于100质量分该(a)不饱和单羧酸,该(b)羟基氨基甲酸酯为5~50质量分。
9.如权利要求1或2的感光性树脂组成物,其特征在于,用于作为光阻涂料。
10.一种干膜光阻,包含盖膜层、如权利要求1至9的任一项的感光性树脂组成物所形成的感光阻剂层,以及隔膜层。
11.一种羟基氨基甲酸酯聚醚化合物,具有如下式(I)的结构:
其中,n为0~10的整数;
R1为如下式(II)~(IV)的混合:
R4为C4-C12的烷基、烯基、炔基、环烷基、聚醚基团或下列式(V):
其中,m为0~5的整数,且
R5为下列结构式:
R2为C4-C12烷基、环烷基、芳香基、聚醚基团、烯胺基;
R3-1~4彼此独立相同或不同,为氢、C4-C12烷基、烯基、环烷基、芳香基、聚醚基团,其中至少含一(甲基)丙烯酸酯基的含不饱和双键基团。
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