TWI492996B - 氟化塗料及以其製得之光工具 - Google Patents
氟化塗料及以其製得之光工具 Download PDFInfo
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Description
本發明揭示一種氟化塗料,特定言之自氟化環氧矽烷(甲基)丙烯酸酯寡聚物製得之氟化塗料。可製造利用該塗料而製得之光工具,且其係用於形成諸如印刷電路板之印刷組件。
於印刷電路工業中,具有呈電路圖形式之圖案的光罩稱為光工具。光敏材料可置於光工具與金屬基板之間,且透過光工具施加輻射,形成呈硬化的光敏材料形式之負圖像。隨後,使硬化與未硬化之光敏材料與光工具分離,並去除任何未硬化之光敏材料,而留置硬化的負圖像於基板上。希望光工具足夠耐用,使得可重複使用,且精確再現電路圖。
本文揭示一種寡聚物、及包含該寡聚物之塗料。該寡聚物可包含環氧乙烷環、可水解矽烷基團、及氟化基團。該塗料包含環氧矽烷與該寡聚物之反應產物。於一些實施例中,該塗料包含:環氧矽烷及一種寡聚物,該寡聚物又包含MF
ME
MS
,其中MF
包含經氟化之(甲基)丙烯酸酯,ME
包含環氧(甲基)丙烯酸酯,且MS
包含矽烷(甲基)丙烯酸酯。
亦揭示一種組件,其包含光工具、氟化塗料、及金屬基板。具有電路圖圖像之光工具可與輻射敏感性材料組合使用,以製造印刷電路板。
亦揭示一種製造印刷組件之方法。該方法可包括:提供光工具,其包含位於提供圖像之光學透明基板上之塗層;提供位於金屬基板上之光阻材料層;隨後使光工具層壓在一起,使得該光阻材料層位於該光工具與金屬基板之間;使該光阻材料層透過該光工具曝露於輻射,藉此使所選區域內之光阻材料層硬化,形成如該光工具中所設計之負圖像。隨後可很容易地使該光工具與已硬化及未硬化之光阻材料層分離或自其脫離,以重複使用。印刷組件可包括印刷電路板。
於製造印刷電路組件期間,必須利用顯微鏡經常且小心地檢查具有電路圖之光工具之表面,以確保表面上無劃痕,例如電路圖之斷裂細線。取決於電路圖之尺寸及複雜程度,此等檢查可花費2至3小時。劃痕及其他磨損可因為經常擦拭光工具之表面以去除灰塵、纖維屑等而出現。此外,光工具通常隔著光敏材料層壓向銅片,因此銅片的小毛邊或粗糙邊緣可在光工具表面上產生劃痕及其他磨損。
由於光工具易於受到刮擦,且磨損在正常使用光工具期間係一個嚴重問題,因此通常使用保護膜及保護層來保護光工具。例如,將塗覆有多種壓敏性黏合劑之聚酯薄膜層壓至具圖像之表面,以保護圖像。然而,由於其之厚度,層壓薄膜可導致光學變形,且因此損失解析度。可藉由以液態組合物塗覆光工具表面而獲得較薄之保護性塗層。塗覆之後,使該液態薄塗層硬化,以產生所需之保護塗層。然而,許多保護性保護層的脫離性能有限,因此會黏合至光阻材料表面,尤其係當存在諸如高黏性焊料光罩油墨之相當黏稠之材料時。雖然具有藉由層壓施加於光工具上之聚矽氧層之薄膜可提供良好的脫離性能,但其柔軟且幾乎不抗刮擦,因此除厚度問題之外,其保護作用有限。
由此可見,需要一種可用於保護表面及標的免受刮擦及磨損,並可用於光工具之塗料組合物或塗料,若塗料可很容易地與諸如焊料光罩油墨之相當黏稠之材料脫離,則較佳。
本文所揭示之塗料可提供抗磨性、硬度、透明度、低表面能及低黏度、脫離性能、抗反射性、抗染色及污染、且防染料、污物、溶劑、油、及水。當塗覆至基板時,塗料相當耐用,比裸露的基板表面本身更抗污染物,且更易於清洗。可使用任意基板,包括諸如天然石材、人造石材、陶瓷、聚乙烯、木材、磚石建築、軟木、玻璃等之硬基板。亦可使用諸如聚(對苯二甲酸乙二酯)、聚碳酸酯及聚甲基丙烯酸甲酯之聚合物基板。
塗料可用於保護光工具免受刮擦及磨損。塗料可具有良好的脫離性能,且甚至當存在諸如焊料光罩之黏稠材料時,亦不會黏合至光阻材料表面。可重複使用具有本文所揭示之塗料的光工具,用於製造許多接觸印刷物,例如光工具可使用至少5、10或20次。
塗料可具有低表面能,且後退水接觸角大於約70°(較佳大於約80°;更佳大於約90°),且後退十六烷接觸角大於約50°(較佳大於約55°,更佳大於約60°)。塗料可具有良好的脫離性能,其係如低的剝離力所證實。
塗料可包含環氧矽烷與一種寡聚物之反應產物,該寡聚物又包含:
MF
ME
MS
其中MF
包含經氟化之(甲基)丙烯酸酯,ME
包含環氧(甲基)丙烯酸酯,且MS
包含矽烷(甲基)丙烯酸酯。
通常如下所述,例如利用光酸產生劑使環氧矽烷固化。環氧矽烷包含至少一可聚合環氧基團、及至少一可聚合矽烷基團。該等可聚合基團中之一個或兩個可為端基。環氧矽烷可為單體、寡聚、或多聚。環氧矽烷可由如下通式表示:
其中:E為具有至少一個環氧乙烷環之有機基團;L1
及L2
獨立地為二價鍵結基團;Rj為多價單體、寡聚、或多聚殘基;Y1
、Y2
及Y3
獨立地為烷基、芳基或可水解基團,其中,Y1
、Y2
及Y3
中之至少一個為可水解基團;x至少為1;且y至少為1。E可包括具有縮水甘油氧基或環氧環己基之有機基團。可水解基團包括具有C1
-C4
烷基之烷氧基。通常,除非特別排除,否則本文中出現之結構通式包含對二價鍵結基團之取代。
L1
及L2
可獨立地包括不可水解之直鏈或分支鏈、環狀或非環狀脂族、芳香族、或脂族及芳香族二價烴鍵結基團。二價鍵結基團可具有20個以下之碳原子或10個以下之碳原子,例如該二價鍵結基團可獨立地包括亞甲基、伸乙基、伸異丙基、伸丁基、伸癸基、伸苯基、伸環己基、伸環戊基、甲基伸環己基、2-乙基伸丁基、乙烯基或丙二烯。L1
及L2
可獨立地包括-C6
H4
-CH2
CH2
-或-CH2
C(CH3
)2
CH2
-。L1
及L2
可獨立地包括醯基,諸如甲醯基、乙醯基、及丙醯基。
L1
及L2
可獨立地包括一個或多個諸如N、O、及S之雜原子,只要不損害塗料之硫化性或性能。適宜之二價鍵結基團可包括醚、酯、醯胺、NO2
、烷氧基、硫醚、碸、及鹵素官能基。L1
及L2
可獨立地包括由如下通式表示之環氧乙烷官能基:-(CH2
CH2
O)k
Z-,其中k為1至10之整數,且Z為具有10以下碳原子之伸烷基。L1
及L2
可獨立地包括-CH2
CH2
-、-CH2
CH2
OCH2
CH2
-、-(CH2
CH2
)2
OCH2
CH2
-、-CH2
OCH2
CH2
-或-CH2
OCH2
CH2
CH2
-。
適用之環氧矽烷可由如下通式表示:
G-L1
-Si(R1
)u
(OR2
)3-u
其中:G為縮水甘油氧基或環氧環己基;L1
為上述二價鍵結;R1
及R2
獨立地為C1
-C4
烷基;且u為0或1。環氧矽烷實例包括縮水甘油氧基甲基三烷氧基矽烷;縮水甘油氧基乙基三烷氧基矽烷;縮水甘油氧基丙基三烷氧基矽烷;縮水甘油氧基丁基三烷氧基矽烷;(3,4-環氧環己基)甲基三烷氧基矽烷;(3,4-環氧環己基)乙基三烷氧基矽烷;(3,4-環氧環己基)丙基三烷氧基矽烷;及(3,4-環氧環己基)丁基三烷氧基矽烷。特定環氧矽烷闡述於Qiu等人之國際專利案第PCT/US2009/036733號中。
環氧矽烷可包括:
G-Si(R1
)u
(OR2
)3-u
其中G、R2
及R3
係如先前段落所述。
環氧矽烷可包括:
G-(CH2
)m
(O)n
(CH2
)p
-Si(OR3
)3
其中:G為縮水甘油氧基或環氧環己基;m為1至6;n為0或1;p為1至6;R3
為H或C1
-C10
烷基。
任一文中所揭示之環氧矽烷的經部份水解衍生物可能適用;該等經部份水解之衍生物包括其中與矽鍵結之烷氧基團經羥基置換之矽烷。任一文中所揭示環氧矽烷之經部份縮合衍生物可能適用;該等經部份縮合之衍生物包括其中與矽鍵結之烷氧基團經矽烷氧基置換之矽烷。例如經部份水解及經部份縮合之衍生物可包括:
G-L1
-Si(OCH3
)3 →
G-L1
-Si(OCH3
)2
(OH)(經部份水解)→
G-L1
-Si(OCH3
)(OH)2
(經部份水解)→
G-L1
-Si(OCH3
)(OH)(OSi(OCH3
)(OH)-L1
-G)(經部份縮合)
經部份水解及/或經部份縮合之衍生物可單獨使用或相互組合使用,及/或與文中揭示之任一種環氧矽烷組合使用。預聚合物之形成法為:如US 4,100,134(Robins等人)及US 7,037,585(Treadway),使除了矽烷之外之基團聚合。
環氧矽烷可自由以下組成之群中選出:γ-縮水甘油氧基丙基三甲氧基矽烷及β-(3,4-環氧環己基)乙基三甲氧基矽烷。
取決於塗料之所需性能,可使用任一所需量之環氧矽烷。例如,環氧矽烷可佔塗料總重量之約50至約90重量%或約70至約90重量%。環氧矽烷亦可佔塗料總重量之約70至約98重量%,或約90至約98重量%。環氧矽烷亦可佔塗料總重量之約50至約95重量%。
寡聚物包含如下之反應產物:MF
ME
MS
其中MF
包含經氟化之(甲基)丙烯酸酯,ME
包含環氧(甲基)丙烯酸酯,且MS
包含矽烷(甲基)丙烯酸酯。另外,該寡聚物包含如下之反應產物:全氟化聚醚(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
經氟化之(甲基)丙烯酸酯可由如下通式表示:Rf
-Q-XC(O)C(R4
)=CH2
其中:Rf
包括單價氟化基團;Q包括二價鍵結基團;X包括O、S、NH或NR5
,其中R5
為C1
-C4
烷基;且R4
包括H或CH3
。
全氟聚醚基團Rf
可為直鏈、分支鏈、環狀、或其組合,且可為飽和或不飽和。全氟聚醚基團Rf
具有至少兩個連接氧原子。全氟聚醚實例包括彼等具有自由如下組成之群中選出之全氟化重複單元者:-(Cq
F2q
)-、-(Cq
F2q
O)-、-(CF(W))-、-(CF(W)O)-、-(CF(W)Cq
F2q
O)-、-(Cq
F2q
CF(W)O)-、-(CF2
CF(W)O)-、或其組合。於該等重複單元中,q通常為1至10之整數。於一些實施例中,q為1至8、1至6、1至4、或1至3之整數。基團W為全氟烷基、全氟醚基團、全氟聚醚、或全氟烷氧基,其均可為直鏈、分支鏈或環狀。W基團通常具有不多於12個碳原子,不多於10個碳原子,不多於9個碳原子,不多於4個碳原子,不多於3個碳原子,不多於2個碳原子,或不多於1個碳原子。於一些實施例中,W基團可具有不多於4個,不多於3個,不多於2個,不多於1個,或無氧原子。於該等全氟聚醚基團中,不同重複單元可沿鏈隨機分佈。
就單價Rf
基團而言,端基可為(Cq
F2q+1
)-、(Cq
F2q+1
O)-、-(VCq
F2q
O)-、或-(VCq
F2q+1
)-,其中q係如先前段落中所述,且V為氫、氯、或溴。單價Rf
基團實例包括CF3
O(C2
F4
O)r
CF2
-及C3
F7
O(CF(CF3
)CF2
O)r
CF(CF3
)-,其中r之平均值為0至50、1至50、3至30、3至15、或3至10。
二價Rf
基團包括-CF2
O(CF2
O)r
(C2
F4
O)s
CF2
-、-(CF2
)3
O(C4
F8
O)s
(CF2
)3
-、-CF2
O(C2
F4
O)s
CF2
-及-CF(CF3
)(OCF2
CF(CF3
))t
OCv
F2v
O(CF(CF3
)CF2
O)s
CF(CF3
)-,其中r係如先前段落中所述;s之平均值為0至50、3至30、3至15、或3至10;t之平均值為0至50、1至50、3至30、3至15、或3至10;總和(n+t)之平均值為0至50或4至40;總和(r+s)大於0;且v為2至6之整數。
當合成時,化合物通常包括Rf
基團之混合物。平均結構為混合組分之平均結構。該等平均結構中之數值r、s、及t可變化,只要基團之數量平均分子重量為至少約300或至少約1000。適用之Rf
基團之分子重量(數量平均)通常為300至5000、800至4000、或1000至5000。
Q可包括以上針對L1
所述之二價鍵結基團。Q可包括共價鍵,例如經氟化之(甲基)丙烯酸酯可包括Rf
-XC(O)C(R4
)=CH2
,諸如Rf
-OC(O)C(R4
)=CH2
。
適宜之經氟化之(甲基)丙烯酸酯實例包括全氟化聚醚(甲基)丙烯酸酯,諸如:C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)CH2
OC(O)CH=CH2
、C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)CH2
OC(O)C(CH3
)=CH2
、C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)CH2
OCH2
CH2
C(O)CH=CH2
、C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)CH2
OCH2
CH2
OC(O)C(CH3
)=CH2
、C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)C(O)NHCH2
CH2
OC(O)CH=CH2
、及C3
F7
O(CF(CF3
)CF2
O)a
CF(CF3
)C(O)NHCH2
CH2
OC(O)C(CH3
)=CH2
,其中a可為1至50。
經氟化之(甲基)丙烯酸酯可由如下通式表示:
Rf
-Q-OC(O)C(R4
)=CH2
其中:Rf
包括C3
F7
O(C3
F6
O)r
CF(CF3
)-,且r為1至30,Q包括二價鍵結基團,且R4
包括H或CH3
。
取決於寡聚物及/或塗料之所需性能,可使用任一所需量之經氟化之(甲基)丙烯酸酯。例如,全氟化聚醚(甲基)丙烯酸酯可佔寡聚物總重量之約5至約60重量%,約5至約50重量%,或約10至約40重量%。
環氧(甲基)丙烯酸酯可由如下通式表示:
G-L1
-OC(O)C(R4
)=CH2
其中:G、L1
及R4
係如上所述。例如,環氧(甲基)丙烯酸酯可包括縮水甘油基(甲基)丙烯酸酯。其他特定環氧(甲基)丙烯酸酯闡述於Qiu等人之國際專利案第PCT/US2009/036733號中。
取決於寡聚物及/或塗料之所需性能,可使用任一所需量之環氧(甲基)丙烯酸酯。例如,環氧(甲基)丙烯酸酯可佔寡聚物總重量之約5至約90重量%,或約10至約60重量%。
矽烷(甲基)丙烯酸酯可由如下通式表示:
(R2
O)3-u
(R1
)u
Si-L1
-OC(O)C(R4
)=CH2
其中L1
、R1
、R2
及R4
係如上所述。矽烷(甲基)丙烯酸酯實例包括丙烯醯氧基丙基三烷氧基矽烷及甲基丙烯醯氧基丙基三烷氧基矽烷。例如,矽烷(甲基)丙烯酸酯可包括γ-甲基丙烯醯氧基丙基三甲氧基矽烷。亦可使用諸如乙烯基三烷氧基矽烷之乙烯系不飽和矽烷。
取決於寡聚物及/或塗料之所需性能,可使用任一所需量之矽烷(甲基)丙烯酸酯。例如,矽烷(甲基)丙烯酸酯可佔寡聚物總重量之約5至約90重量%,或約10至約60重量%。
塗料可進一步包含多官能環氧化物。適用之多官能環氧化物包括彼等具有環脂族官能基者。多官能環氧化物可自由以下組成之群中選出:雙-(3,4-環氧環己基甲基)己二醛酯;1,4-環己烷二甲醇二縮水甘油基醚;及甘油丙氧基三縮水甘油基醚。多官能環氧化物可包括雙-(3,4-環氧環己基甲基)己二酸酯及1,4-環己烷二甲醇二縮水甘油基醚。其他多官能環氧化物闡述於Qiu等人之申請案第PCT/US2009/036733號中。
取決於塗料之所需性能,可使用任一所需量之多官能環氧化物。例如,多官能環氧化物可佔塗料總重量之約0.05至約30重量%或約0.05至約20重量%。多官能環氧化物亦可佔塗料總重量之約0.02至約15重量%,或約0.05至約10重量%。
可使用單體製備該寡聚物,其中經氟化之(甲基)丙烯酸酯佔寡聚物總重量之約5至約60重量%,環氧(甲基)丙烯酸酯佔約5至約90重量%,且矽烷(甲基)丙烯酸酯佔約5至約90重量%。
可使用寡聚物製備塗料,其中:寡聚物佔塗料總重量之約0.005至約20重量%。適用之塗料可具有:佔塗料總重量之約50至約95重量%之環氧矽烷,及約0.005至約20重量%之寡聚物。適用之塗料具有:佔塗料總重量之約50至約95重量%之環氧矽烷,約0.05至約30重量%之多官能環氧化物,及約0.005至約20重量%之寡聚物。
塗料可進一步包含由如下通式表示之可固化矽烷:
Si(R6
)d
(R7
)4-d
其中:R6
包括烷基、芳基、芳基伸烷基或烷基伸芳基,R7
包括鹵素、羥基、芳氧基、醯氧基或聚伸烷基氧基,且d為0、1或2;且該可固化矽烷佔塗料總重量之約0.005至約30重量%。
塗料可進一步包含原矽酸四乙酯(TEOS)。
塗料可進一步包含:多官能環氧化物、及由如下通式表示之可固化矽烷:
Si(R6
)d
(R7
)4-d
其中:R6
包括烷基、芳基、芳基伸烷基或烷基伸芳基,R7
包括鹵素、羥基、芳氧基、醯氧基或聚伸烷基氧基,且d為0、1或2。
寡聚物可包含:
MF
ME
MS
其中MF
包含經氟化之(甲基)丙烯酸酯,ME
包含環氧(甲基)丙烯酸酯,且MS
包含矽烷(甲基)丙烯酸酯。
用於形成塗料之組分可包含:環氧矽烷、及一種寡聚物,該寡聚物又包含:
MF
ME
MS
其中MF
包含經氟化之(甲基)丙烯酸酯,ME
包含環氧(甲基)丙烯酸酯,且MS
包含矽烷(甲基)丙烯酸酯。
寡聚物可包含:環氧乙烷環、可水解矽烷基團、及氟化基團。可使用大體上由該寡聚物組成之塗料。
該寡聚物包含如下物質之反應產物:經氟化之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯、或全氟化聚醚(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。該寡聚物之製法通常為:於存在一種或多種鏈轉移劑下,令該等單體發生自由基聚合反應。適宜鏈轉移劑包括例如經羥基-、胺基-、巰基、矽烷及鹵素取代之有機化合物,諸如四溴甲烷及如下物質之經巰基取代之衍生物:乙烷、丙烷、丁烷、辛烷、十二烷、丙醇、丁醇、丙二醇、乙胺等。鏈轉移劑之通常存在量應足以控制聚合單體單元之數量及寡聚物之分子量,例如其量為每當量單體約0.005當量至約0.5當量。
可使用不具有矽烷及環氧官能基之其他(甲基)丙烯酸酯以製備該寡聚物。其他(甲基)丙烯酸酯可含有不會與矽烷及環氧基發生反應之官能基。代表性(甲基)丙烯酸酯為丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、2-溴乙基丙烯酸酯、丙烯酸正丁基酯、丙烯酸第三丁基酯、丙烯酸己酯、丙烯酸正辛基酯、甲基丙烯酸正辛基酯、丙烯酸異辛基酯、丙烯酸十八烷基酯、甲氧基聚乙二醇單甲基丙烯酸酯、丙烯酸四氫糠基酯、烷氧基化四氫糠基丙烯酸酯、丙烯酸月桂基酯、烷氧基化月桂基丙烯酸酯、2-苯氧基乙基丙烯酸酯、丙烯酸薄荷基酯、丙烯酸正苄基酯、丙烯酸十三烷基酯、己內酯丙烯酸酯、丙烯酸異冰片基酯、烷氧基化苯酚丙烯酸酯、聚丙二醇單丙烯酸酯、丙烯腈、2-氰乙基丙烯酸酯、1H,1H,2H,2H-全氟化丁基丙烯酸酯、1H,1H,2H,2H-全氟化己基丙烯酸酯、及甲基乙烯基酮。
可利用諸如購自DuPont公司之VAZO產品的聚合引發劑來製備寡聚體。其他適宜聚合引發劑包括偶氮化合物,諸如偶氮雙異丁腈(AIBN)、氫過氧化物、過氧化物等。
可於適於進行有機自由基反應之任一溶劑中進行聚合反應以形成寡聚物。單體可以任一適宜濃度存在於溶劑中,包括例如反應混合物總重量之約5重量%至約90重量%。適宜溶劑包括例如脂族、脂環族及芳香族烴、醚、酯、酮、亞碸等。可基於如下考慮因素選擇溶劑:諸如試劑之溶解度、使用特定引發劑所需之溫度、及所需之分子量。適用於進行聚合反應之溫度為約30至約200℃。
可採用光酸產生劑或陽離子型光引發劑,並結合UV輻射來製備塗料。適用之陽離子型光引發劑包括多種經芳基取代之化合物之鹽,例如芳香族鎓鹽,諸如Va、VIa及VIIa族元素之鹽。陽離子型光引發劑為購自Ciba Geigy Co.之CYRACURE產品,例如CYRACURE UVI-6974。其他陽離子型光引發劑係闡述於Qiu等人之國際專利案第PCT/US2009/036733號中。陽離子型引發劑通常佔本發明組合物之約1%至約5重量%。
較佳自不含溶劑之塗料組合物形成塗料。然而於一些實施例中,組合物包含溶劑,諸如例如酮(例如丙酮、甲基乙基酮(MEK)或甲基異丁基酮(MIBK))、酯(例如乙酸乙酯、甲基異丁基醚、或碳酸丙烯酯)、或醚(例如甲基第三丁基醚(MTBE)或四氫呋喃(THF))、或其組合。
塗料可進一步包含交聯劑以固化及交聯環氧-矽烷塗料調配物中之環氧及矽烷基團。可添加交聯劑,以進一步控制硬度或塗料品質。1,4-環己烷二甲醇二縮水甘油基醚(CDDE)為適宜之交聯劑之實例。
塗料可包含可固化矽烷、鈦酸鹽及鋯酸鹽。例如,諸如四烷基原矽酸鹽之矽酸鹽使用量可為塗料總重量之至多約40重量%。其他可固化添加劑包括四甲氧基矽烷、四乙氧基矽烷、甲基三乙氧基矽烷、二甲基二乙氧基矽烷、十八烷基三乙氧基矽烷、甲基三氯矽烷、四甲基原鈦酸鹽、四乙基原鈦酸鹽、四異丙基原鈦酸鹽、四乙基鋯酸鹽、四異丙基鋯酸鹽、及四丙基鋯酸鹽。
塗料可應用於任一類型之適宜基板,例如包含天然石材、人造石材、陶瓷、乙烯基物、木材、磚石建築物、軟木、玻璃、塑膠等之基板。於一些實施例中,基板可包括光學透明基板,其對可見光及紫外光具低霧度(例如小於約5%或甚至小於約2%)及高透明度(例如大於95%或大於98%)。光學透明基板可包含玻璃、熔凝矽石、聚對苯二甲酸乙二酯(PET)、聚碳酸酯、或聚甲基丙烯酸(甲)酯。
塗料可以大體上不改變位於其下之基板的外觀(諸如光特性)之量存在於基板之上。塗料厚度可為約0.5至約40微米、約2至約15微米或約2至約10微米。於一些情形中,例如當塗料為單層唯一塗料時,厚度可為約1至約100微米。若塗層包含一層層疊加之多層,則最上層可比其下之層體薄得多。例如,最上層可為約20埃至約1微米或約40至約100 nm。適用之塗層總厚度(包括多層塗層中之所有層體)可為任一適宜厚度,包括例如約0.5至約40微米、或約1至約5微米。若使用多層,則其等可具有相同或不同之組成。
可採用任一適用方法或技術以任一適宜形式(包括連續或不連續層)將塗料組合物施用於基板,該等方法或技術包括例如噴、刷、擦、刮塗、凹口塗佈、逆輥塗佈、凹槽輥塗佈、浸泡、浸漬塗佈、棒塗佈、溢流塗佈、旋轉塗佈及其組合。最終所得之塗層亦可呈多種形式,包括例如連續或不連續層(例如呈一圖案、點、條及渦旋)。
於塗佈期間或之後,採用諸如UV輻射之輻射使塗料組合物固化或至少部份固化。若存在溶劑,則可至少部份去除溶劑(例如,採用強制空氣烘箱;通過於高溫及周溫下之蒸發;及其組合),隨後使組合物至少部份固化,以形成塗層。
本文所揭示之塗料可用於製造光工具。適用之光工具包括彼等其中塗層位於光學透明基板上者。光學透明基板包含圖像,諸如採用數位成像系統所形成之電路圖。藉由將光敏材料或光阻材料沉積於金屬基板上而形成組件,其中塗層及光敏材料相互毗鄰。光敏材料可包含照相乳液層,其包含鹵化銀或偶氮乳液。亦可使用鉻金屬吸收薄膜。金屬基板可包含銅片。隨後使組件曝露於輻射,使得光敏材料固化(顯影及固定),形成硬化部份,其形成光工具上之圖像。於一些位置,使光工具與固化之後之光敏材料分離。洗滌、乾燥、檢查且視需要修飾已硬化光敏材料之負圖像。
因此,本發明揭示一種製造諸如印刷電路板之印刷組件之方法。該方法包括:提供一種先前段落中所述之組件,使光阻材料層透過光工具曝露於輻射,藉此使所選區域內之光阻材料層硬化,形成由光學透明基板所提供之圖像的負圖像。該方法可進一步包括使光工具與已硬化光阻材料層分離。
藉由以下實例進一步闡述本發明之標的及優點,但於該等實例中所採用之特定材料及其數量、及其他條件及細節不應過度限制本發明。
實例中所用之材料出示於表1中。
於IPA浴中,於手動攪拌下漂洗經塗布之薄膜1分鐘,並乾燥隨後測量水及十六烷接觸角。採用購自AST Products(Billerica,MA)之VCA-2500XE視頻接觸角分析機進行測量。所記錄之數值為至少兩液滴之平均值,且對各液滴測量兩次。用於靜態測量之液滴體積為5 μL,且用於前進及後退測量時為1-3 μL。
使用Sharpie特大號永久標記筆(King Size Permanent Marker)、Sharpie永久標記筆(Permanent Marker)及Vis--vis永久高空工程用筆(Permanent Overhead Project Pen)(均購自Sanford,Oak Brook,IL)在已固化之塗層上作標記。肉眼評估墨水,並自5(油墨完全形成小珠)至1(不形成小珠)評分。
採用可沿薄膜表面振盪固定至觸針之鋼絲絨之機械裝置,沿與塗佈方向橫向之方向測試固化薄膜之耐刮擦性。觸針係以3.5次刮掃/秒之速率在10 cm刮掃寬度範圍內振盪。一次刮掃之定義為10 cm單程。觸針具有直徑為3.8 mm之平底圓柱幾何圖形,且具有400 g壓力。鋼絲絨係以商品名「#0000-Super-Fine」購自Rhodes-American(Homax Products,Bellingham,WA之分公司),且直接使用。每種組合物測試一次,且每次測試係由以400 g壓力刮掃50次組成。於此測試之後,利用Sharpie永久標記筆進行抗標記物測試,並於刮擦表面上測量水接觸角及十六烷接觸角。
取一滴(直徑約1.25 cm)有機溶劑置於已固化塗層上。讓溶劑於室溫下蒸發至乾,並肉眼評估塗層。「透明」之評估結果說明為對塗層無可見損害之透明表面,而「模糊」說明模糊之表面。此外,利用Sharpie永久標記筆進行抗標記物測試,以測試溶劑經乾燥之斑點。
使用由Bausch&Lomb製得之Sight Savers由IPA預濕潤之拭鏡紙擦拭固化表面20次。擦拭表面並乾燥之後,採用Sharpie永久標記筆對擦拭區域進行抗標記物測試。並肉眼觀察擦拭表面,並評定為透明或模糊。
肉眼評定塗層品質,並評定為極佳、佳、一般或稍許反濕潤。
向4盎司瓶子添加3.0 g HFPO-MAr、1.0 g GMA、6.0 g A-174、0.045 g CBr4
、30 g EtOAc、及0.25 g Vazo-67。向該混合物鼓入氮氣1分鐘,隨後密封該瓶子,並於磁力攪拌下加熱該混合物至70℃,並保持24小時。獲得透明均質溶液。FTIR分析指出幾乎所有CH2
=CMe-均已反應。最終所得之溶液含有約25%固形物。
利用下列組分,以與FAO-1類似之方式製得FAO-2:3.0 g HFPO-MAr、2.0 g GMA、5.0 g A-174、0.021 g CBr4
、30 g EtOAc、及0.21 g Vazo-67。
利用下列組分,以與FAO-1類似之方式製得FAO-3:3.0 g HFPO-MAr、3.0 g GMA、4.0 g A-174、0.025 g CBr4
、30 g EtOAc、及0.20 g Vazo-67。
利用下列組分,以與FAO-1類似之方式製得FAO-4:3.0 g HFPO-MAr、4.0 g GMA、3.0 g A-174、0.035 g CBr4
、30 g EtOAc、及0.22 g Vazo-67。
利用下列組分,以與FAO-1類似之方式製得FAO-5:3.0 g HFPO-MAr、5.0 g GMA、2.0 g A-174、0.033 g CBr4
、30 g EtOAc、及0.20 g Vazo-67。
利用下列組分,以與FAO-1類似之方式製得FAO-6:3.0 g HFPO-MAr、6.0 g GMA、1.0 g A-174、0.035 g CBr4
、30 g EtOAc、及0.22 g Vazo-67。
利用下列組分,以與FAO-1類似之方式製得FAO-7:4.0 g HFPO-MAr、1.0 g GMA、5.0 g A-174、0.068 g CBr4
、30 g EtOAc、及0.19 g Vazo-67。
代表性環氧-矽烷(ES)塗料調配物之製法為:依下列重量比混合各組分。
藉由組合並混合各組分製得各調配物。將所有調配物塗佈於具有6號線條之有底聚酯(Melinex 618,DuPont,Wilmington,DE)上,於120℃下乾燥2分鐘,並利用下列其中一種UV源固化。調配物通常透明,說明全氟化聚醚胺基甲酸酯矽烷添加劑與環氧-矽烷塗料調配物的相容性良好。
UV-1:於N2
下之H-Bulb,依每分鐘20英尺之速率掃描兩次
UV-2:於空氣中,以兩個Sylvania Germicidal G15T8燈泡(15W)照射2分鐘
UV-3:於空氣中,以兩個黑光藍色UV燈泡(F15T8BLB15W)照射2分鐘
代表性調配物實例及性能數據概括於下表中。所有調配物均係以重量%計。
大體上由寡聚物及光引發劑組成之塗料的測試結果概括於表2中。
[a]以UV-2固化所有調配物
[b]測試順序:特大號/永久/Vis--vis
大體上由環氧-矽烷及寡聚物組成之塗料的測試結果概括於表3中。
[a]測試順序:特大號/永久/Vis--vis
[b]以UV-2固化調配物;[c]以UV-3固化;[d]以UV-1固化
[e]購自日本Sekisui Chemical之以矽酮為基底之脫離襯
如表3所示,對比於比較調配物C-1至C-4,向環氧-矽烷調配物添加2至5%全氟化聚醚丙烯酸酯可顯著改善抗標記物性能及接觸角。於許多實例中,抵抗性能係與表2中所示之純環氧-矽烷全氟化聚醚丙烯酸酯寡聚物之抵抗性能類似。
含有交聯劑之代表性調配物之測試結果顯示於表4中。
[a]以UV-2固化所有調配物
[b]測試順序:特大號/永久/Vis--vis
如表4所示,添加TEOS或CDDE交聯劑後,未觀察到對性能之顯著影響。
作為保護性塗層,重要的在於塗層應耐受可能存在於清洗溶液中之溶劑。作為脫離襯,重要的在於襯應耐受可能存在於黏合劑中之溶劑。測試一些試驗調配物(E-1至E-10、E-12、E-13、E-15、E-18、E-21、E-22、E-24、E-26、E-28、E-30、E-32、E-34、E-36、E-38)與下列溶劑之相容性:EtOAc、IPA、丙酮、甲苯、MEK、DMF。對於所有測試溶劑,於溶劑蒸發後,評定膜為「透明」,且抗Sharpie永久標記物性能評定為5。
除了耐溶劑性,塗層必須提供抗刮擦保護。於代表性經塗佈薄膜上進行鋼絲絨耐用性測試,且結果顯示於表5中。
[a]測試順序:特大號/永久/Vis--vis
[b]以200 g重量刮擦4次之後,具有可見刮痕
如表5所示,所有實例調配物均顯示良好抗刮擦性。此外,經刮擦後之區域維持抗標記物性能及高接觸角。反之,未經塗佈之脫離襯未顯示鋼絲絨刮擦抗性,且顯示不佳的抗標記物性能。
亦研究膠帶脫離性。樣本之製法為:層壓測試膠帶845(Scotch845書帶,購自3M公司)或610(Scotch610保險玻璃帶,購自3M公司)至本發明之固定於位於鋼板上之PET薄膜上之塗層。利用2.3 kg橡膠輥向塗層施覆膠帶。隨後以180°之角度並以2.3 m/min之速率自塗層剝離膠帶。所有測試均係於恒溫(70℉)及恒濕(50%RH)下進行。使用獲自IMASS,Inc.,Accord,Massachusetts之IMass型SP2000剝離測試機進行測量。表6概括含FAO-7之ES-1及ES-3塗層的代表性剝離結果。
如表6所示,相較於彼等無氟化添加劑之塗層,向ES-1或ES-3添加2%或更多環氧-矽烷HFPO丙烯酸酯寡聚物之後,剝離力顯著減小。
文中所引用之公開案的全部揭示內容係以引用的方式全部併入文中,其程度就好像其等分別各自併入一般。於不脫離本發明之範圍及精神下,彼等熟習此項技術者咸瞭解可對本發明進行多種修改及改變。應瞭解,本發明無意受文中所出示之闡述性實施例及實例之過度限制,且該等實例及實施例僅係以舉例之方式出示,且本發明之範圍僅意欲受如下之本文所出示之專利申請範圍限制。
Claims (22)
- 一種塗料,其包含如下各物之反應產物:(a)環氧矽烷;及(b)一種寡聚物,其包含如下各物之反應產物:經氟化之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
- 如請求項1之塗料,其中該環氧矽烷係自由如下組成之群中選出:γ-縮水甘油氧基丙基三甲氧基矽烷及β-(3,4-環氧環己基)乙基三甲氧基矽烷。
- 如請求項1之塗料,其中該經氟化之(甲基)丙烯酸酯係由如下通式表示:Rf -Q-OC(O)C(R4 )=CH2 其中:Rf 包括C3 F7 O(C3 F6 O)r CF(CF3 )-,且r為1至30,Q包括二價鍵結基團,及R4 包括H或CH3 。
- 如請求項1之塗料,其中該環氧(甲基)丙烯酸酯包含縮水甘油基(甲基)丙烯酸酯。
- 如請求項1之塗料,其中該矽烷(甲基)丙烯酸酯包含γ-甲基丙烯醯氧基丙基三甲氧基矽烷。
- 如請求項1之塗料,該塗料進一步包含:(c)多官能環氧化物。
- 如請求項6之塗料,其中該多官能環氧化物係自由如下組成之群中選出:雙-(3,4-環氧環己基甲基)己二酸酯;1,4-環己烷二甲醇二縮水甘油基醚;及甘油丙氧基化三 縮水甘油醚。
- 如請求項1之塗料,其中:相對於寡聚物之總重量,該經氟化之(甲基)丙烯酸酯佔約5至約60重量%,該環氧(甲基)丙烯酸酯佔約5至約90重量%,及該矽烷(甲基)丙烯酸酯佔約5至約90重量%。
- 如請求項1之塗料,其中:該寡聚物係佔塗料總重量之約0.005至約20重量%。
- 如請求項1之塗料,其中:相對於塗料之總重量,該環氧矽烷佔約50至約95重量%,及該寡聚物佔約0.005至約20重量%。
- 如請求項6之塗料,其中:相對於塗料之總重量,該環氧矽烷佔約50至約95重量%,該多官能環氧化物佔約0.05至約30重量%,及該寡聚物佔約0.005至約20重量%。
- 如請求項1之塗料,其進一步包含:(d)由如下通式表示之可固化矽烷:Si(R6 )d (R7 )4-d 其中:R6 包括烷基、芳基、芳基伸烷基或烷基伸芳基;R7 包括鹵化物、羥基、芳氧基、醯氧基或聚伸烷基氧基;且d為0、1或2;且該可固化矽烷佔該塗料總重量之約0.005至約30重量%。
- 如請求項1之塗料,其進一步包含:(e)四乙基原矽酸酯。
- 如請求項1之塗料,其進一步包含:(c)多官能環氧化物,及(d)由如下通式表示之可固化矽烷:Si(R6 )d (R7 )4-d 其中:R6 包括烷基、芳基、芳基伸烷基或烷基伸芳基;R7 包括鹵化物、羥基、芳氧基、醯氧基或聚伸烷基氧基;且d為0、1或2。
- 一種寡聚物,其包含如下物質之反應產物:全氟化聚醚(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
- 一種組合物,其包含如下物質之反應產物:(a)環氧矽烷;及(b)一種寡聚物,其包含:經氟化之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
- 一種寡聚物,其包含:環氧乙烷環、可水解之矽烷基團、及全氟化聚醚基團。
- 一種物件,其包含設置於基板上之塗層,該塗層包含如 請求項1之塗料,且厚度為約0.5至約40μm。
- 一種組件,其包含:光工具,其包含提供圖像之光學透明基板;金屬基板;及設置於該光工具與該金屬基板之間之塗層,其中該塗層包含如請求項1之塗料。
- 一種物件,其包含:圖像層,該層包含如下物質之反應產物:(a)環氧矽烷;及(b)一種寡聚物,其包含如下物質之反應產物:經氟化之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
- 一種組合物,其包含:(a)環氧矽烷;及(b)一種寡聚物,其包含:經氟化之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、及矽烷(甲基)丙烯酸酯。
- 如請求項21之組合物,其進一步包含光酸產生劑。
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EP (1) | EP2478034A1 (zh) |
KR (1) | KR101768237B1 (zh) |
CN (1) | CN102549042B (zh) |
TW (1) | TWI492996B (zh) |
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Also Published As
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EP2478034A1 (en) | 2012-07-25 |
WO2011034845A1 (en) | 2011-03-24 |
TW201124484A (en) | 2011-07-16 |
CN102549042A (zh) | 2012-07-04 |
KR20120069717A (ko) | 2012-06-28 |
US20120171433A1 (en) | 2012-07-05 |
US9051423B2 (en) | 2015-06-09 |
KR101768237B1 (ko) | 2017-08-14 |
CN102549042B (zh) | 2015-01-28 |
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