201207555 六、發明說明: 【發明所屬之技術領域】 本發明係關於可藉鹼性水溶液顯像之光硬化性熱硬化 性樹脂組成物,尤其是藉紫外線曝光或雷射曝光而光硬化 之抗焊劑用組成物,其乾膜及硬化物,以及具有使用彼等 形成之硬化皮膜之印刷配線板。 【先前技術】 目前,一部份之民生用印刷配線板以及大部份產業用 之印刷配線板之阻焊劑,就高精度、高密度之觀點而言, 係使用紫外線照射後,藉由顯像形成圖像,藉熱及/或光 照射達到修飾硬化(正式硬化)之液狀顯像型阻焊劑,基 於對環境問題之考量,以使用鹼性水溶液作爲顯像液之鹼 顯像型之光阻劑成爲主流,且實際上大量使用於印刷配線 板之製造。又,對應於近年來電子設備之輕薄短小化所伴 隨之印刷配線板之高密度化,亦要求阻焊劑之作業性且高 性能化。 然而,現有之鹼顯像型光阻劑,在耐久性方面而言仍 有問題。亦即,相較於過去之熱硬化型、溶劑顯像型者, 其耐鹼性、耐水性、耐熱性等均差。其原因認爲係鹼顯像 型光阻焊劑爲了可藉鹼顯像而以具有親水性基者作爲主成 分,而容易滲透藥液、水、水蒸氣等,使耐藥品性降低或 光阻皮膜與銅之密著性降低之故。結果,作爲耐藥品性之 耐鹼性變弱,尤其是BGA (球格柵陣列)或CSP (晶粒尺 201207555 寸封裝)等半導體封裝中尤其需要亦稱爲耐濕熱性之pct 耐性(壓力鍋試驗(Pressure Cooker Test)),但現狀爲 在該等嚴格條件下亦僅能達到數小時至數十小時左右。且 ,在加濕條件下施加電壓之狀態下之H A S T試驗(高度加 速壽命試驗)中,大多數情況下,在數小時內確認到因移 行發生引起之缺陷。 且近幾年來,朝表面安裝之轉移,且對環境問題之疑 慮所伴隨之無鉛焊料之使用等,有對封裝施加極高溫度之 傾向。伴隨於此,封裝內外部之到達溫度顯著變高,以過 去的液狀感光性阻劑,會有因熱經歷造成塗膜劣化或特性 產生變化,發生剝離,有如前述之PCT或HAST耐性變差之 問題,而要求其改良》 另一方面,過去之阻焊劑中所使用之含有羧基之樹脂 —般係使用藉由環氧樹脂之改質而衍生之環氧基丙烯酸酯 改質樹脂。例如,特開昭6 1 -243 869號公報(專利文獻1 ) 中報導有包含於酚醛清漆型環氧化合物與不飽和單元酸之 反應產物上加成酸酐之感光性樹脂、光聚合起始劑、稀釋 劑及環氧化合物之阻焊劑組成物。且,特開平3-250012號 公報(專利文.獻2 )中揭示包含於使水楊醛與一價酚之反 應產物與表氯醇反應所得之環氧樹脂上加成(甲基)丙烯 酸,接著與多元羧酸或其酸酐反應而得之感光性樹脂、光 聚合性起始劑、有機溶劑等之阻焊劑組成物。 如上述之環氧丙烯酸酯改質樹脂會大量殘留源自環氧 丙烯酸酯之羥基,而有原先之耐水性惡化之問題。 201207555 [先前技術文獻] [專利文獻] [專利文獻1]特開昭6卜243869號公報 [專利文獻2]特開平3-250012號公報 【發明內容】 [發明欲解決之課題] 本發明係鑒於如前述之以往技術問題而完成者,其目 的係提供一種光硬化性熱硬化性樹脂組成物,其係要求在 高溫之熱經歷的半導體封裝用阻焊劑,可形成具有重要的 PCT耐性、HAST耐性、無電解電鍍耐性、冷熱衝擊耐性之 硬化皮膜。 進而本發明之目的係提供一種藉由使用該光硬化性熱 硬化性樹脂組成物獲得之如上述諸特性優異之乾膜及硬化 物,以及由該乾膜或硬化物形成阻焊等之硬化皮膜之印刷 配線板。 [用以解決課題之手段] 爲達成前述目的,依據本發明,提供一種可藉由鹼性 水溶液顯像之光硬化性熱硬化性樹脂組成物,其特徵爲含 有:含羧基之樹脂(但’以環氧樹脂作爲起始原料之含羧 基之樹脂除外)、光聚合起始劑,及具有萘環之環氧樹脂 201207555 上述含有羧基之樹脂較好具有感光性基。 再者依據本發明係提供一種將前述光硬化性熱硬化性 樹脂組成物塗佈於載體薄膜上並經乾燥獲得之光硬化性熱 硬化性乾膜,以及使前述光硬化性熱硬化性樹脂組成物或 乾膜硬化,較好以波長3 50nm〜410nm之光源予以光硬化成 圖型狀所得之硬化物。 又另外,依據本發明,提供一種印刷配線板,其具有 以活性能量線照射,較好以紫外線直接描繪,而使前述光 硬化性熱硬化性樹脂組成物或乾膜光硬化成圖型狀後,經 熱硬化而得之硬化皮膜》 [發明效果] 本發明之光硬化性熱硬化性樹脂組成物由於使用不以 環氧樹脂作爲起始原料之含有羧基之樹脂,含有與其組合 之含有萘環之環氧樹脂作爲可藉由鹼性水溶液顯像之成分 ,故不僅硬化塗膜之強韌性、耐熱性獲得提高,而且塗膜 經熱經歷後,以及過硬化時之物性變化少。而且出乎意料 之外地發現即使熱硬化溫度低仍具有良好之硬化性,進而 即使在高溫度下施加熱經歷,物性亦無變化,而維持良好 之特性。據此,藉由使用本發明之光硬化性熱硬化性樹脂 組成物,可形成具有作爲半導體封裝用阻焊劑爲重要的 PCT耐性、HAST耐性、無電解電鍍耐性 '優異的耐熱性之 硬化皮膜。 201207555 【實施方式】 如前述所示’本發明之光硬化性熱硬化性樹脂組成物 之特徵爲含有不以環氧樹脂作爲起始原料之含羧基之樹脂 、光聚合起始劑及含萘環之環氧樹脂。 至於上述含有羧基之樹脂,若爲不以環氧樹脂作爲起 始原料之含有羧基之樹脂,則可使用以往習知之各種含有 殘基之樹脂’但其中,就光硬化性或耐顯像性方面而言, 較好爲分子中具有乙烯性不飽和雙鍵之含有羧基之感光性 樹脂。因此’其不飽和雙鍵較好爲源自丙烯酸或甲基丙烯 酸或該等之衍生物者。又,僅使用沒有乙烯性不飽和雙鍵 之含有羧基之樹脂時,爲了使組成物成爲光硬化性,故需 要倂用如後述之分子中具有一個以上之乙烯性不飽和基之 化合物(感光性單體)。 本發明中可使用之含有羧基之樹脂之具體例較好爲以 下所列舉之化合物(寡聚物及聚合物之任一種)。 (1) 於使雙酚A、雙酚F、雙酚S、酚醛清漆型酚樹脂 、聚-對羥基苯乙烯、萘酚與醛類之縮合物、二羥基萘與 醛類之縮合物等之一分子中具有兩個以上酚性羥基之化合 物,與環氧乙烷、環氧丙烷等環氧烷反應獲得之反應產物 中,使(甲基)丙烯酸等含有不飽和基之單羧酸反應,於 所得之反應產物中,使馬來酸酐 '四氫苯二甲酸酐、偏苯 三酸酐、均苯四酸酐、己二酸等多元酸酐反應所得之含有 羧酸之感光性樹脂。 (2) 於使一分子中具有兩個以上之酚性羥基之化合 9 - 201207555 物與碳酸乙烯酯、碳酸丙烯酯等環狀碳酸酯化合物反應所 得之反應產物中,使含有不飽和基之單羧酸反應,於所得 反應產物中,使多元酸酐反應所得之含有羧基之感光性樹 脂。 (3) 藉由脂肪族二異氰酸酯、分支脂肪族二異氰酸 酯、脂環式二異氰酸酯、芳香族二異氰酸酯等二異氰酸酯 化合物,與聚碳酸酯系多元醇、聚醚系多元醇、聚酯系多 元醇、聚烯烴系多元醇、丙烯酸系多元醇、雙酚A系環氧 烷加成物二醇、具有酚性羥基及醇性羥基之化合物等之二 醇化合物之聚加成反應所得之胺基甲酸酯樹脂之末端與酸 酐反應而得之末端含有羧基之胺基甲酸酯樹脂。 (4) 於藉由使二異氰酸酯與二羥甲基丙酸、二羥甲 基丁酸等含有羧基之二醇化合物及二醇化合物之聚加成反 應獲得之含有羧基之胺基甲酸酯樹脂之合成中,添加(甲 基)丙烯酸羥基烷酯等分子中具有一個羥基與一個以上之 (甲基)丙烯醯基之化合物之末端經(甲基)丙烯酸化之 含有羧基之胺基甲酸酯樹脂。 (5) 於藉由使二異氰酸酯與含有羧基之二醇化合物 及二醇化合物之聚加成反應所得之含有羧基之胺基甲酸酯 樹脂之合成中,添加異佛爾酮二異氰酸酯與季戊四醇三丙 烯酸酯之等莫耳反應物等之分子中具有一個異氰酸酯基與 一個以上之(甲基)丙烯醯基之化合物之末端經(甲基) 丙烯酸化之含有羧基之胺基甲酸酯樹脂。 (6) 藉由(甲基)丙烯酸等不飽合羧酸與苯乙烯、 -10- 201207555 α-甲基苯乙烯、(甲基)丙烯酸低級烷酯、異丁烯等含有 不飽合基之化合物之共聚合所得之含有羧基之樹脂。 (7) 對如後述之多官能基氧雜環丁烷樹脂,使己二 酸、苯二甲酸、六氫苯二甲酸等二羧酸反應,於生成之一 級羥基上加成苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲 酸酐等二元酸酐而成之含有羧基之聚酯樹脂中,進一步加 成(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸α-甲基縮 水甘油酯等一分子中具有一個環氧基與一個以上(甲基) 丙烯醯基之化合物而成之含有羧基之感光性樹脂》 (8) 於前述(1)〜(7)之含有羧基之樹脂上加成一 分子中具有環狀醚基與(甲基)丙烯醯基之化合物而成之 含有羧基之感光性樹脂。 又,本說明書中,所謂(甲基)丙烯酸酯爲總稱丙烯 酸酯、甲基丙烯酸酯及該等之混合物之用語,對於其他類 似之表現亦同。 本發明中使用之含羧基之樹脂之特徵爲由於不使用環 氧樹脂作爲起始原料,故鹵化物含量極少》本發明中使用 之含有羧基之樹脂之氯離子雜質含量爲0〜lOOppm,較好爲 0〜50ppm,更好爲0〜30ppm。 另外,本發明中使用之含有羧基之樹脂可容易地獲得 不含羥基之樹脂。已知一般而言羥基之存在亦具有因氫鍵 而導致密著性提高等優點特徵,但會使耐濕性顯著下降。 以下說明與一般之阻焊劑中使用之環氧基丙烯酸酯系改質 樹脂比較之本發明之含羧基樹脂之優點。 -11 - 201207555 沒有氯成分之酚酚醛清漆樹脂可容易取得。此可藉由 環氧烷改質之酚樹脂之部分之丙烯酸化,以及酸酐之導入 ,獲得雙鍵當量3 00〜5 5 0,酸價40〜120 mgKOH/g之範圍內 之理論上無羥基之樹脂。 另一方面,由類似之酚酚醛清漆樹脂所合成之環氧樹 脂之環氧基全部經丙烯酸化,對全部羥基導入酸酐時,在 雙鍵當量400-500時酸價變得極大,無法獲得曝光後仍具 有耐顯像性之塗膜。而且,由於酸價高,故耐水性差,使 絕緣信賴性、PCT耐性顯著降低。亦即,由於由類似之酚 酚醛清漆型環氧樹脂衍生之環氧基丙烯酸酯系改質之樹脂 極難以成爲完全沒有羥基。 據此,過去之環氧基丙烯酸酯系改質之樹脂無法避免 地具有羥基,但羥基之存在不僅對吸水性之觀點,亦影響 環氧樹脂與酸之反應性。亦即,已知羥基會促進酸與環氧 基之反應,但可預測羥基之存在直至硬化物形成凝膠化前 之際,促進效果雖高,但反應系統在凝膠化後其促進效果 變弱。亦即,存在多數羥基之系統中之酸與環氧基之反應 被認爲到達反應終點變慢而非反應過早開始。於反應太早 開始方面,就組成物之可使用時間或使溶劑乾燥直到顯像 之前之顯像壽命之觀點而言並不好,進而由於凝膠化在較 早階段形成故直至反應完成爲止於高溫長時間變得必要。 本發明之組成物由於係以無羥基存在之狀態下反應,故反 應爲溫和反應。其結果被認爲顯像之前之壽命變長,而且 反應容易完成。結果被認爲可獲得優異之信賴性者。該現 -12- 201207555 像在使用後述之含有萘環之環氧樹脂時更顯著看到。此被 認爲係由於含有萘環之環氧樹脂之萘環爲平面構造故熔融 黏度低,使反應性變高所帶來之影響。 又,胺基甲酸酯樹脂亦可藉由配合羥基與異氰酸酯基 之當量,而容易地合成不含羥基之樹脂。較佳之樹脂爲不 使用碳醯氯(Phosgene)作爲起始原料之異氰酸酯化合物 ,由不使用表氯醇之原料所合成之氯離子雜質量在 0〜30ppm之含有羧基之樹脂,更好爲合成爲理論上不含羥 基之樹脂。 由該等觀點,可最好地使用先前以具體例所示之含有 羧基之樹脂(1)〜(5)。 又,對於藉由與先前所示之含有不飽和基之化合物共 聚合所得之含有羧基之樹脂(6),使作爲一分子中具有 環狀醚基與(甲基)丙烯醯基之化合物之甲基丙烯酸3,4-環氧基環己基甲酯反應而成之含有羧基之感光性樹脂,由 於使用脂環式環氧基故氯離子雜質少,亦可較好地使用。 另一方面,於含有羧基之樹脂(6)中使作爲一分子 中具有環狀醚基及(甲基)丙烯醯基之化合物的甲基丙烯 酸縮水甘油酯反應而成者,或使作爲含有不飽和基之化合 物的甲基丙烯酸縮水甘油酯共聚合而成者,會有氯離子雜 質量變多之顧慮。另外,胺基甲酸酯樹脂合成之際亦可使 用環氧基丙烯酸酯改質原料作爲二醇化合物。雖然會有氯 離子雜質混入,但由於可控制氯離子之雜質量故仍可能使 用 -13- 201207555 如上述之含有羧基之樹脂由於主鏈•聚合物之側鏈上 具有多數游離羧基,故成爲可藉由鹼性水溶液顯像。 又,上述含有羧基之樹脂之酸價較好爲40〜150 mgKOH/g之範圍,更好爲40〜130 mgKOH/g之範圍。含有 羧基之樹脂之酸價若未達40 mgKOH/g則鹼顯像變困難, 另一方面,當超過150 mgKOH/g時由於以顯像液曝光部之 溶解過快,故使線(Line )變的比所需者更細,由於該情 況,曝光部與未曝光部無區別地由顯像液溶解並剝離,因 此正常之光阻圖型描繪變困難故而較不適當。 又,上述含有羧基之樹脂之重量平均分子量,雖隨樹 脂骨架而有所不同,但通常爲2,000~1 50,000,又以5,000〜 1 00,000之範圍者較佳。當重量平均分子量未達2,000時, 有不黏觸性性能劣化之情況,曝光後之塗膜之耐濕性變差 ,於顯像時產生膜減少,而使解像度大幅變差。另一方面 ,當重量平均分子量超過1 50,000時,有顯像性顯著惡化 ,且有儲存安定性變差之情況。 該等含有羧基之樹脂之調配量,在全部組成物中較好 爲20~60質量%,更好爲30〜50質量%。少於上述範圍時, 有塗膜強度降低之情況故較不佳。另一方面,多於上述範 圍時,黏性變高,有塗佈性等降低之情況因而較不佳。 將本發明之樹脂組成物組成於光硬化性樹脂組成物或 光硬化性熱硬化性樹脂組成物中時,可調配光聚合起始劑 。較佳之起始劑可使用由具有肟酯基之肟酯系光聚合起始 劑、α-胺基苯乙酮系光聚合起始劑、醯基磷氧化物系光聚 -14- 201207555 合起始劑組成之群選出之一種以上之光聚合起始劑。 肟酯系光聚合起始劑列舉之市售品爲日本汽巴公司製 造之 CGI-325、Irgacure (註冊商標)OXEOl、Irgacure OXE02、Adeka公司製造之N-1919、NCI-831等。另外,分 子中具有兩個肟酯基之光聚合起始劑亦適用。具體而言列 舉爲以下述通式表示之具有咔唑構造之肟酯化合物。201207555 VI. Description of the Invention: [Technical Field] The present invention relates to a photocurable thermosetting resin composition which can be imaged by an aqueous alkaline solution, particularly a photo-curing agent which is photohardened by ultraviolet exposure or laser exposure. A composition, a dry film and a cured product thereof, and a printed wiring board having a hardened film formed using the same. [Prior Art] At present, some of the printed wiring boards for the people's livelihood and the solder resists of most industrial printed wiring boards are based on high-precision and high-density. Forming an image, and applying a heat-curable (or formally hardened) liquid-based development type solder resist by heat and/or light irradiation, based on environmental considerations, using an alkaline aqueous solution as an alkali-developing type of developing liquid Resistors have become mainstream, and are actually used in large quantities for the manufacture of printed wiring boards. In addition, in response to the recent increase in the density and thickness of electronic devices, the density of printed wiring boards has increased, and the workability and performance of solder resists have been required. However, the conventional alkali developing type photoresist is still problematic in terms of durability. That is, compared with the conventional thermosetting type and solvent developing type, the alkali resistance, water resistance, heat resistance and the like are inferior. The reason why it is considered that the alkali-developing type photoresist has a hydrophilic base as a main component and can easily penetrate a chemical liquid, water, water vapor, etc., so that chemical resistance is lowered or a photoresist film is used. The adhesion with copper is reduced. As a result, the alkali resistance as a chemical resistance is weakened, and in particular, a semiconductor package such as a BGA (ball grid array) or a CSP (grain ruler 201207555 inch package) particularly needs a pct resistance also known as heat and humidity resistance (pressure cooker test) (Pressure Cooker Test)), but the current situation can only reach hours to tens of hours under these strict conditions. Further, in the H A S T test (high acceleration life test) in a state where a voltage is applied under humidification conditions, in most cases, defects due to the occurrence of migration are confirmed within a few hours. In recent years, there has been a tendency to apply extremely high temperatures to packages due to the shift in surface mounting and the use of lead-free solders associated with environmental concerns. Along with this, the temperature of the inside and the outside of the package is remarkably high. In the past, the liquid photosensitive resist may cause deterioration of the coating film or change in characteristics due to thermal history, and peeling may occur, as the aforementioned PCT or HAST resistance is deteriorated. On the other hand, the carboxyl group-containing resin used in the past solder resists is generally an epoxy acrylate-modified resin derived from the modification of an epoxy resin. For example, a photosensitive resin and a photopolymerization initiator which are added to an acid anhydride of a reaction product of a novolac type epoxy compound and an unsaturated unit acid are reported in JP-A-61-243 869 (Patent Document 1). Solder resist composition of thinner and epoxy compound. Further, an epoxy resin-added (meth)acrylic acid obtained by reacting a reaction product of salicylaldehyde with a monovalent phenol with epichlorohydrin is disclosed in Japanese Laid-Open Patent Publication No. Hei-3-250012 (Patent No. 2). Next, a solder resist composition such as a photosensitive resin, a photopolymerizable initiator, or an organic solvent obtained by reacting with a polyvalent carboxylic acid or an anhydride thereof. The above-mentioned epoxy acrylate-modified resin has a large amount of residual hydroxyl groups derived from epoxy acrylate, and has a problem that the original water resistance is deteriorated. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The object of the prior art is to provide a photocurable thermosetting resin composition which is required to have a high resistance to heat and a solder resist for semiconductor encapsulation, and which can form an important PCT resistance and HAST resistance. Hardened film with no electroplating resistance and thermal shock resistance. Further, an object of the present invention is to provide a dry film and a cured product which are excellent in the above properties obtained by using the photocurable thermosetting resin composition, and a hardened film in which a dry film or a cured product is formed into a solder resist or the like. Printed wiring board. [Means for Solving the Problem] In order to achieve the above object, according to the present invention, there is provided a photocurable thermosetting resin composition which can be developed by an aqueous alkaline solution, which comprises a carboxyl group-containing resin (but ' A resin containing a carboxyl group as a starting material, a photopolymerization initiator, and an epoxy resin having a naphthalene ring 201207555 The above carboxyl group-containing resin preferably has a photosensitive group. According to the present invention, there is provided a photocurable thermosetting dry film obtained by applying the photocurable thermosetting resin composition onto a carrier film and dried, and comprising the photocurable thermosetting resin. The material or the dry film is hardened, and the cured product obtained by photohardening into a pattern is preferably used with a light source having a wavelength of from 3 50 nm to 410 nm. Further, according to the present invention, there is provided a printed wiring board which is irradiated with an active energy ray, and is preferably directly drawn by ultraviolet rays, and the photocurable thermosetting resin composition or the dry film is photohardened into a pattern. (The effect of the invention) The photocurable thermosetting resin composition of the present invention contains a carboxyl group-containing resin which does not use an epoxy resin as a starting material, and contains a naphthalene ring in combination therewith. Since the epoxy resin is a component which can be imaged by an aqueous alkaline solution, not only the toughness and heat resistance of the cured coating film are improved, but also the physical properties of the coating film after heat treatment and under hardening are small. Further, it has been unexpectedly found that even if the heat hardening temperature is low, it has good hardenability, and even if heat is applied at a high temperature, the physical properties are not changed, and good characteristics are maintained. By using the photocurable thermosetting resin composition of the present invention, it is possible to form a cured film having excellent heat resistance such as PCT resistance, HAST resistance, and electroless plating resistance which are important as a solder resist for semiconductor encapsulation. 201207555 [Embodiment] As described above, the photocurable thermosetting resin composition of the present invention is characterized by containing a carboxyl group-containing resin, a photopolymerization initiator, and a naphthalene ring containing no epoxy resin as a starting material. Epoxy resin. As the carboxyl group-containing resin, a resin containing a carboxyl group which does not use an epoxy resin as a starting material can be used in various conventionally known residues-containing resins, but in terms of photocurability or development resistance. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in its molecule is preferred. Therefore, the unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or such derivatives. Further, when only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a compound having one or more ethylenically unsaturated groups in a molecule to be described later (photosensitivity). monomer). Specific examples of the carboxyl group-containing resin which can be used in the present invention are preferably the following compounds (any of an oligomer and a polymer). (1) A condensate of bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, etc. a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, and reacting a monocarboxylic acid having an unsaturated group such as (meth)acrylic acid, A carboxylic acid-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as maleic anhydride 'tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic acid into the obtained reaction product. (2) In a reaction product obtained by reacting a compound having 9 or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, a single unit containing an unsaturated group is used. The carboxylic acid is reacted to obtain a photosensitive resin containing a carboxyl group obtained by reacting a polybasic acid anhydride with the obtained reaction product. (3) A diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester polyol Amino group obtained by polyaddition reaction of a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group A urethane resin having a carboxyl group at the terminal obtained by reacting the terminal of the acid ester resin with an acid anhydride. (4) A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate with a diol compound containing a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid, and a diol compound In the synthesis, a (meth)acrylated carboxyl group-containing urethane having a terminal having a hydroxyl group and one or more (meth)acrylinyl groups in a molecule such as a hydroxyalkyl (meth)acrylate is added. Resin. (5) In the synthesis of a carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate with a diol compound containing a carboxyl group and a diol compound, isophorone diisocyanate and pentaerythritol are added. A (meth) acrylated carboxyl group-containing urethane resin having a terminal of a compound having one isocyanate group and one or more (meth) acrylonitrile groups in a molecule such as an acrylate. (6) A compound containing an unsaturated group such as (meth)acrylic acid and unsaturated carboxylic acid and styrene, -10- 201207555 α-methylstyrene, lower alkyl (meth)acrylate, isobutylene or the like The resulting carboxyl group-containing resin is copolymerized. (7) A polyfunctional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form a phthalic anhydride on the primary hydroxyl group. Further, a polyester resin containing a carboxyl group formed by a dibasic acid anhydride such as tetrahydrophthalic anhydride or hexahydrophthalic anhydride is further added with glycidyl (meth)acrylate or α-methyl shrinkage (meth)acrylate. a photosensitive resin containing a carboxyl group and a compound having one epoxy group and one or more (meth)acryloyl group in one molecule, such as a glyceride, (8) a carboxyl group-containing resin according to the above (1) to (7) A photosensitive resin containing a carboxyl group formed by adding a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule. Further, in the present specification, the term "(meth)acrylate" is a term generally referred to as acrylate, methacrylate, and the like, and is similar to other similar expressions. The carboxyl group-containing resin used in the present invention is characterized in that since the epoxy resin is not used as a starting material, the halide content is extremely small. The carboxyl group-containing resin used in the present invention has a chloride ion impurity content of 0 to 100 ppm, preferably. It is 0 to 50 ppm, more preferably 0 to 30 ppm. Further, the resin containing a carboxyl group used in the present invention can easily obtain a resin containing no hydroxyl group. It is known that in general, the presence of a hydroxyl group also has an advantage of improving adhesion due to hydrogen bonding, but the moisture resistance is remarkably lowered. The advantages of the carboxyl group-containing resin of the present invention in comparison with the epoxy acrylate-based modified resin used in a general solder resist will be described below. -11 - 201207555 Phenolic novolak resins without chlorine are readily available. This can be obtained by acrylation of a portion of the phenol resin modified with an alkylene oxide, and introduction of an acid anhydride to obtain a double bond equivalent of 00 to 5,500, and a theoretically non-hydroxyl group in the range of an acid value of 40 to 120 mgKOH/g. Resin. On the other hand, the epoxy group of the epoxy resin synthesized from a similar phenol novolak resin is all acrylated, and when an acid anhydride is introduced to all of the hydroxyl groups, the acid value becomes extremely large at a double bond equivalent of 400 to 500, and exposure cannot be obtained. After that, it still has a coating film resistant to development. Further, since the acid value is high, the water resistance is poor, and the insulation reliability and PCT resistance are remarkably lowered. That is, since the epoxy acrylate-modified resin derived from a similar phenol novolak type epoxy resin is extremely difficult to be completely free of hydroxyl groups. Accordingly, the epoxy-modified acrylate-modified resin in the past has unavoidably possessed a hydroxyl group, but the presence of a hydroxyl group affects the reactivity of the epoxy resin with an acid not only from the viewpoint of water absorption. That is, it is known that a hydroxyl group promotes the reaction between an acid and an epoxy group, but the presence of a hydroxyl group can be predicted until the gelation of the hardened material, and the promotion effect is high, but the promoting effect of the reaction system after gelation is changed. weak. That is, the reaction of the acid with the epoxy group in the system in which a plurality of hydroxyl groups are present is considered to be slow to reach the end of the reaction, rather than starting prematurely. In terms of the start of the reaction too early, it is not preferable from the viewpoint of the usable time of the composition or the drying of the solvent until the development life before development, and further, since the gelation is formed at an early stage until the reaction is completed. High temperatures become necessary for a long time. Since the composition of the present invention reacts in the absence of a hydroxyl group, the reaction is a mild reaction. As a result, it is considered that the life before the development becomes longer, and the reaction is easy to complete. As a result, it is considered that an excellent reliability person can be obtained. The present -12-201207555 is more noticeable when using an epoxy resin containing a naphthalene ring as described later. This is considered to be because the naphthalene ring containing the epoxy resin of the naphthalene ring has a planar structure, so that the melt viscosity is low and the reactivity is increased. Further, the urethane resin can be easily synthesized into a resin containing no hydroxyl group by blending the equivalent of a hydroxyl group and an isocyanate group. The preferred resin is an isocyanate compound which does not use carbon ruthenium (Phosgene) as a starting material, and a carboxyl group-containing resin having a chloride ion mass of 0 to 30 ppm synthesized from a raw material which does not use epichlorohydrin is more preferably synthesized. A resin that theoretically does not contain a hydroxyl group. From these viewpoints, the resin (1) to (5) containing a carboxyl group as exemplified in the specific examples can be preferably used. Further, a resin having a carboxyl group-containing resin (6) obtained by copolymerization with a compound containing an unsaturated group as described above is used as a compound having a cyclic ether group and a (meth)acryl fluorenyl group in one molecule. The photosensitive resin containing a carboxyl group obtained by reacting a 3,4-epoxycyclohexylmethyl acrylate is preferably used because it has a small amount of chlorine ion impurities due to the use of an alicyclic epoxy group. On the other hand, in the resin (6) containing a carboxyl group, a glycidyl methacrylate which is a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule is reacted, or When a saturated group of compounds is copolymerized with glycidyl methacrylate, there is a concern that the amount of chlorine ions is increased. Further, when the urethane resin is synthesized, an epoxy acrylate-modified raw material may be used as the diol compound. Although chloride ion impurities may be mixed, it may be used because it can control the impurity quality of chloride ions.-13-201207555 The carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the main chain polymer. It was developed by an aqueous alkaline solution. Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 150 mgKOH/g, more preferably 40 to 130 mgKOH/g. If the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, when it exceeds 150 mgKOH/g, the dissolution of the exposure portion of the developing solution is too fast, so that the line is formed. In this case, the exposed portion and the unexposed portion are dissolved and peeled off by the developing solution without distinction, and thus the normal photoresist pattern drawing becomes difficult and is less appropriate. Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is usually 2,000 to 150,000, and preferably 5,000 to 1,000,000. When the weight average molecular weight is less than 2,000, the non-tack property is deteriorated, and the moisture resistance of the coating film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 1 50,000, the development property is remarkably deteriorated, and the storage stability is deteriorated. The compounding amount of the carboxyl group-containing resin is preferably from 20 to 60% by mass, more preferably from 30 to 50% by mass, based on the total amount of the composition. When it is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when it is more than the above range, the viscosity is high, and the coating property or the like is lowered, which is not preferable. When the resin composition of the present invention is composed of a photocurable resin composition or a photocurable thermosetting resin composition, a photopolymerization initiator can be added. A preferred initiator can be obtained by using an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a fluorenyl phosphorus oxide photopolymer-14-201207555. One or more photopolymerization initiators selected from the group consisting of initiators. Commercially available products of the oxime ester photopolymerization initiator are CGI-325 manufactured by Ciba Corporation of Japan, Irgacure (registered trademark) OXEO1, Irgacure OXE02, N-1919 manufactured by Adeka Co., Ltd., NCI-831, and the like. Further, a photopolymerization initiator having two oxime ester groups in the molecule is also suitable. Specifically, it is an oxime ester compound having a carbazole structure represented by the following formula.
(式中,X表示氫原子、碳數1~17之烷基、碳數之烷氧 基、苯基、苯基(經碳數1〜17之烷基、碳數1~8之烷氧基 、胺基、具有碳數1〜8之烷基之烷基胺基或二烷基胺基取 代)、萘基(經碳數1~17之烷基、碳數1~8之烷氧基、胺 基、具有碳數1〜8之烷基之烷基胺基或二烷基胺基取代) ,Y、Z各獨立表示氫原子、碳數1〜17之烷基、碳數1〜8之 烷氧基、鹵基、苯基、苯基(經碳數1〜17之烷基、碳數 1~8之烷氧基、胺基、具有碳數1~8之烷基之烷基胺基或二 烷基胺基取代)、萘基(經碳數1〜17之烷基、碳數1〜8之 院氧基 '胺基、具有碳數1~8之院基之院基fl女基或一院基 胺基取代)、蒽基、吡啶基、苯并呋喃基、苯并噻吩基, Ar表示鍵結、或碳數1~1〇之伸烷基、伸乙嫌基、伸苯基、 伸聯苯基、伸吡啶基、伸萘基、噻嗯基、伸蒽基、伸噻吩 -15- 201207555 基、伸呋喃基、2,5-吡咯-二基、4,4,-二苯乙烯(stilbene )二基、4,2’-苯乙烯二基,η爲0或1之整數)。 尤其前述通式中,X、Υ分別爲甲基或乙基,Ζ爲甲基 或苯基,η爲O’ Ar較好爲鍵結,或伸苯基、伸萘基、噻嗯 基或伸噻吩基。 該等聘醋系光聚合起始劑之調配量,相對於上述含有 羧基之樹脂100質量份,較好爲〇·〇1~5質量份。當未達〇.〇1 質量份時’光硬化性不足,造成塗膜剝離、同時耐藥品性 等之塗膜特性降低。另一方面,當超過5質量份時,塗膜 表面上之光吸收變強,而有深部硬化性降低之傾向。更好 爲0.5~3質量份。 α-胺基苯乙酮系光聚合起始劑具體而言列舉爲2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙酮-1、2-苄基-2-二甲胺 基-1-(4 -嗎啉基苯基)-丙-1·酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1·[4-(4 -嗎啉基)苯基]-1-丁酮、Ν,Ν-二甲基胺基苯乙酮等。市售品列舉爲日本汽巴公司製造之 Irgacure 907、Irgacure 3 69、Irgacure 3 79等。 醯基磷氧化物系光聚合起始劑具體而言列舉爲2,4,6-三甲基苯甲醯基二苯基磷氧化物、雙(2,4,6-三甲基苯甲 醯基)-苯基磷氧化物、雙(2,6-二甲氧基二苯甲醯基)-2,4,4-三甲基-戊基磷氧化物等。市售品列舉爲BASF公司製 造之LUCILIN TPO、日本汽巴公司製造之Irgacure 819等 〇 該等α-胺基苯乙酮系光聚合起始劑、醯基磷氧化物系 -16- 201207555 光聚合起始劑之調配量,相對於上述含有羧基之樹脂100 質量份,較好爲0.01〜15質量份。當未達0.01質量份時’同 樣的於銅上之光硬化性不足,造成塗膜剝離、同時耐藥品 性等之塗膜特性降低。另一方面,當超過15質量份時,無 法獲得降低氣體釋出之效果,進而使塗膜表面上之光吸收 變強,而有深部硬化性降低之傾向。更好爲0.5〜10質量份 〇 除此之外,本發明之樹脂組成物可使用之光聚合起始 劑,或光起始助劑及增感劑,可列舉爲苯偶因化合物、苯 乙酮化合物、蒽醌化合物、噻噸酮化合物、縮酮化合物、 二苯甲酮化合物、三級胺化合物及咕噸酮化合物等。 苯偶因化合物具體而言列舉爲例如苯偶因、苯偶因甲 基醚、苯偶因乙基醚、苯偶因異丙基醚等。 苯乙酮化合物具體而言列舉爲例如苯乙酮、2,2-二甲 氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二 氯苯乙酮等。 蒽醌化合物具體而言列舉爲例如2-甲基蒽醌、2-乙基 蒽醌、2-第三丁基蒽醌、1-氯蒽醌等。 噻噸酮化合物具體而言列舉爲例如2,4-二甲基噻噸酮 、2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二異丙基噻噸酮 等。 縮酮化合物具體而言列舉爲例如苯乙酮二甲基縮酮、 苄基二甲基縮酮等。 二苯甲酮化合物具體而言列舉爲例如二苯甲酮、4 -苯 -17- 201207555 甲醯基二苯基硫醚、4-苯甲醯基-4’·甲基二苯基硫醚、4-苯甲醯基-4’-乙基二苯基硫醚、4-苯甲醯基- 4’-丙基二苯基 硫酸等。 三級胺化合物具體而言列舉爲例如乙醇胺化合物、具 有二烷基胺基苯構造之化合物,例如,市售品列舉爲4,4 ’ -二甲基胺基二苯甲酮(日本曹達公司製造之NISSOKUA MABP) 、4,4’-二乙基胺基二苯甲酮(保土谷化學公司製 造之EAB)等二烷基胺基二苯甲酮、7-(二乙胺基)-4 -甲 基-2H-1-苯并吡喃-2-酮(7-(二乙胺基)-4-甲基香豆素) 等含二烷基胺基之香豆素化合物、4-二甲胺基苯甲酸乙酯 (曰本化藥公司製造之KAYAKUA (註冊商標)EPA) 、2-二甲基胺基苯甲酸乙酯(國際生物合成公司製造之 Quantacure DMB) 、4-二甲胺基苯甲酸(正丁氧基)乙酯 (國際生物合成公司製造之Quantacure BEA)、對-二甲 胺基苯甲酸異戊基乙酯(日本化藥公司製造之KAYAKUA-DMBI) 、4-二甲胺基苯甲酸2-乙基己酯(Van Dyk公司製 造之Esolol 507) 、4,4’-二乙基胺基二苯甲酮(保土谷化 學公司製造之EAB )等。 該等中,以噻噸酮化合物及三級胺化合物較佳。尤其 ,若含有噻噸酮化合物,就深部硬化性方面而言較佳,其 中較好含有2,4 -二甲基噻噸酮、2,4_二乙基噻噸酮、2 -氯 噻噸酮、2,4 -二異丙基噻噸酮等噻噸酮化合物。 該等噻噸酮化合物之調配量相對於前述含羧酸之樹脂 100質量份’較好爲20質量份以下》當噻噸酮化合物之調 -18- 201207555 配量超過20質量份時,膜厚硬化性降低,且與製品成本提 高有關。更好爲10質量份以下。 至於三級胺化合物,較好爲具有二烷基胺基苯構造之 化合物,其中最佳者爲二烷基胺基二苯甲酮化合物、最大 吸收波長爲350~450nm之含有二烷基胺基之香豆素化合物 及酮基香豆素類。 至於二烷基胺基二苯甲酮化合物,4,4’-二乙基胺基二 苯甲酮因毒性低而較佳。含有二烷基胺基之香豆素化合物 ,由於最大吸收波長在3 50~410nm及紫外線範圍內,因此 著色少,於原本無色透明之感光性組成物,使用著色顔料 ,可提供反映著色顏料本身顏色之著色膜。尤其,以7-( 二乙胺基)-4-甲基-2H-1-苯并吡喃-2-酮較佳。 該等三級胺化合物之調配量相對於前述含羧基之樹脂 1〇〇質量份,較好爲0.1〜20質量份。當三級胺化合物之調 配量未達0.1質量份時,有無法獲得足夠增感效果之傾向 。當超過20質量份時,會有深部硬化性降低之傾向。更好 爲0.1〜10質量份。 該等光聚合起始劑、光起始助劑與增感劑可單獨使用 或以兩種以上之混合物使用。 該等光聚合起始劑、光起始助劑及增感劑之總量,相 對於前述含羧基之樹脂100質量份,以成爲35質量份以下 較佳。當超過35質量份時,由於該等之光吸收而有深部硬 化性降低之傾向。 又,該等光聚合起始劑、光起始助劑及增感劑由於吸 -19- 201207555 收特定之波長,故某些情況下之感度下降,會有作爲以紫 外線吸收劑之作用。然而,該等並非用於提高組成物之感 度而使用者。視需要吸收特定波長之光,可提高表面之光 反應性,使塗膜之線形狀及開口變成垂直、角錐狀、倒角 錐狀,同時提高線寬與開口徑之加工精度。 前述光聚合起始劑中最佳者爲由具有肟酯基之肟酯系 光聚合起始劑、α-胺基苯乙酮系光聚合起始劑、醯基磷氧 化物系光聚合起始劑所組成群組選出之一種以上之光聚合 起始劑。該等中肟酯系光聚合起始劑由於起始劑效率良好 ,少量即可有效的提高感度,故光阻皮膜形成後知熱處理 時因氣體釋出造成之污染或揮發少,有效的降低皮膜之翹 曲故較佳。另外咕噸酮系、香豆素系之增感劑對於調整光 阻之剖面形狀有效故較佳。最好爲倂用二者。 本發明之光硬化性熱硬化性樹脂組成物中使用之含有 萘環之環氧樹脂除了先前總體之反應性良好,提早完成反 應以外,可獲得對熱經歷強之高耐熱塗膜,另外所得硬化 塗膜之線熱膨脹係數(以下簡稱爲CTE )不會下降,對於 阻焊劑硬化時之應力緩合極爲有效。該含有萘環之環氧樹 脂列舉爲例如HP-403 2 ( DIC (股)製造)、ΗΡ-4700 ( DIC (股)製造)、ESN-3 55 (東都化成(股)製造)、 ESN-3 75 (東都化成(股)製造)、NC-73 00 (日本化藥 (股)製造)等。可最適用者列舉爲具有萘環骨架、及芳 烷基構造等之多官能型環氧樹脂或其衍生物。 含有萘環之環氧樹脂之調配量相對於前述含有羧基之 -20- 201207555 樹脂100質量份,以5質量份至60質量份以下較佳,更好爲 10質量份以上,50質量份以下。未達5質量份無法確認含 有萘環之環氧樹脂之效果,另一方面,超過60質量份時塗 膜之觸黏性惡化,會有引起顯像不良之虞故不適當。 另外本發明之光硬化性熱硬化性樹脂組成物可添加熱 硬化性成分以賦予耐熱性。本發明中使用之熱硬化性成分 可使用經保護之異氰酸酯化合物、胺基樹脂、馬來醯亞胺 化合物、苯并噁嗪樹脂、碳二醯亞胺樹脂、環碳酸酯化合 物、多官能基環氧化合物、多官能基氧雜環丁烷化合物、 環硫化物(episulfide)樹脂、三聚氰胺衍生物等習知慣用 之熱硬化性樹脂。該等中較佳之熱硬化成分爲一分子中具 有2個以上之環狀醚基及/或環狀硫醚基(以下簡稱爲環狀 (硫)醚基)之熱硬化性成分。該等具有環狀(硫)醚基 之熱硬化性成分市售之種類相當多,可依據其構造而賦予 多樣之特性。 該等分子中具有2個以上之環狀(硫)醚基之熱硬化 性成分爲分子中具有兩個以上之3、4或5員環狀醚基、或 環狀硫醚基之任一者或兩種基之化合物,例如分子內具有 至少2個以上環氧基之化合物,亦即多官能性環氧化合物 ’分子內具有至少2個以上之氧雜環丁烷基之化合物,亦 即多官能性氧雜環丁烷化合物,分子內具有2個以上硫醚 基之化合物,亦即環硫化物樹脂等。 至於前述多官能性環氧化合物,列舉有例如日本環氧 樹脂公司製造之jER (註冊商標)828、jER834、jER1001 -21 - 201207555 、jER 1004,DIC公司製造之Epiclon (註冊商標)840、 Epiclon 850、Epiclon 1050、Epiclon 2055,東都化成公司 製造之 EPOTOT (註冊商標)YD-011、YD-013、YD-127、 YD-128,道化學公司製造之 D.E.R.317、D.E.R.331、 D.E.R.661、D.E.R.664,日本汽巴公司之 Araldide 6071、 Araldide 6084、Araldide GY250、Araldide GY260’ 住友 化學工業公司製造之Sumi-epoxy ESA-011、ESA-014、 E LA-115、ELA-128,旭化成工業公司製造之A.E.R.330、 A.E.R.331、A.E.R.661、A.E.R.664 等(均爲商品名)之雙 酚A型環氧樹脂;日本環氧樹脂公司製造之jERYL 903, DIC公司製造之Epiclon 152、Epiclon 165,東都化成公司 製造之EPOTOT YDB-400、YDB-5 00 -道化學公司製造之 D.E.R.542,日本汽巴公司之Araldide 8011,住友化學公 司製造之Sumi-epoxy ESB-400、ESB-700,旭化成工業公 司製造之八.£.11.711、八.£.11.714等(均爲商品名)之溴化 環氧樹脂;日本環氧樹脂公司製造之jER 152、jER 154,道 化學公司製造之D.E.N.431、D.E.N.438,DIC公司製造之 Epiclon N-730、Epiclon N-770、Epiclon N-865,東都化 成公司製造之EPOTOT YDCN-701、YDCN-704,曰本汽巴 公司製造之 Araldide ECN 1 23 5、Araldide ECN 1 273、 Araldide ECN1299、Araldide XPY307,日本化藥公司製造 之EPPN (註冊商標)-201、EOCN (註冊商標)- 1 025、 EOCN-1020、EOCN-104S > RE-306,住友化學工業公司製 造之 Sumi-epoxy ESCN-195X、ESCN-220,旭化成工業公 -22- 201207555 司製造之A.E.R. ECN-235、ECN-299等(均爲商品名)之 酚醛清漆型環氧樹脂;DIC公司製造之Epiclon 830’日本 環氧樹脂公司製造之jER807,東都化成公司製造之 EPOTOT YDF-170、YDF-175、YDF-2004,日本汽巴公司 製造之Araldide XPY306等(均爲商品名)之雙酚F型環氧 樹脂;東都化成公司製造之EPOTOT ST-2004、ST-2007、 ST-3 000 (商品名)等之氫化雙酚A型環氧樹脂;日本環氧 樹脂公司製造之jER604,東都化成公司製造之EPOTOT YH-434,曰本汽巴公司製造之Araldide MY720,住友化學 工業公司製造之Sumi-epoxy ELM-120等(均爲商品名)之 縮水甘油胺型環氧樹脂;日本汽巴公司製造之Araldide CY-3 5 0 (商品名)等之乙內醯脲型環氧樹脂;Dicel化學 工業公司製造之Celloxide (註冊商標)202 1,日本汽巴公 司製造之Araldide CY 175 ' CY 179等(均爲商品名)之脂 環式環氧樹脂;日本環氧樹脂公司製造之YL-933,道化學 公司製造之T.E.N·,ΕΡΡΝ·501、ΕΡΡΝ-502等(均爲商品名 )之三羥基苯基甲烷型環氧樹脂;日本環氧樹脂公司製造 之YL-605 6、ΥΧ-4000、YL-6121 (均爲商品名)等之雙二 甲苯酚型或聯酚型環氧樹脂或該等之混合物;日本化藥公 司製造之EBPS-200,ADEKA公司製造之ΕΡχ_30,DIC公司 製造之ΕΧΑ-1514 (商品名)等之雙酚δ型環氧樹脂;日本 環氧樹脂公司製造之jER157S (商品名)等之雙酚a酣酸清 漆型環氧樹脂;日本環氧樹脂公司製造之jERYL-931,日 本汽企公司製造之Araldide 163等(均爲商品名)之四苯 -23- 201207555 醯基乙烷型環氧樹脂;日本汽巴公司製造之Araldide PT810 (商品名),日產化學工業公司製造之TEPIC (註 冊商標)之雜環式環氧樹脂;日本油脂公司製造之 Blenmer (註冊商標)DGT等二縮水甘油基苯二甲酸酯樹 脂:東都化成公司製造之ZX- 1 063等四縮水甘油基二甲苯 醯基乙烷樹脂;新日鐵化學公司製造之ESN-190、ESN-3 60,DIC 公司製造之 HP-4032、EXA-4750、EXA-4700 等含 萘基之環氧樹脂;DIC公司製造之HP-7200、HP-7200H等 具有二環戊二烯骨架之環氧樹脂;日本油脂公司製造之 CP-50S、CP-50M等縮水甘油基甲基丙烯酸酯共聚物系環 氧樹脂;進而有環己基馬來西亞胺與縮水甘油基甲基丙烯 酸酯之共聚合環氧樹脂;環氧改質之聚丁二烯橡膠衍生物 (例如,Dicel化學工業製造之PB-3600等)、CTBN改質之 環氧樹脂(例如,東都化成公司製造之YR-102、YR-450 等)等,但並不限於該等。該等環氧樹脂可單獨使用或組 合兩種以上使用。該等中尤其以酚醛清漆型環氧樹脂、改 質之酚醛清漆型環氧樹脂、雜環式環氧樹脂、雙酚型環氧 樹脂或該等之混合物較佳》 前述多官能基氧雜環丁烷化合物列舉爲雙[(3-甲基· 3-氧雜環丁基甲氧基)甲基]醚、雙[(3-乙基-3-氧雜環丁 基甲氧基)甲基]醚' 1,4-雙[(3-甲基-3-氧雜環丁基甲氧 基)甲基]苯、1,4-雙[(3-乙基-3-氧雜環丁基甲氧基)甲 基]苯、丙烯酸(3 -甲基-3-氧雜環丁基)甲酯、丙烯酸( 3-乙基-3-氧雜環丁基)甲酯、甲基丙烯酸(3-甲基-3-氧 -24 - 201207555 雜環丁基)甲酯、甲基丙烯酸(3-乙基-3-氧雜環丁基)甲 酯或該等之寡聚物或共聚物等多官能性氧雜環丁烷類,以 及氧雜環丁烷醇與酚醛清漆樹脂、聚(對-羥基苯乙烯) 、CALDO型雙酚類、杯芳烴類、間苯二酚杯芳烴( calixresorcinarene )類、或倍半矽氧烷等具有羥基之樹脂 之醚化物等。另外,列舉爲具有氧雜環丁烷環之不飽和單 體與(甲基)丙烯酸烷酯之共聚物等。 前述分子中具有2個以上環狀(硫)醚基之環硫化物 化合物列舉爲例如日本環氧樹脂公司製造之YL7000 (雙酚 A型環硫化物樹脂),或東都化成(股)製造之YSLV-120TE等。又,亦可使用利用同樣之合成方法,以硫原子 取代酚醛清漆型環氧樹脂之環氧基之氧原子之環硫化物樹 脂等。 前述分子中具有2個以上環狀(硫)醚基之熱硬化性 成分之調配率’相對於前述含有羧基之樹脂之羧基1當量 ,較好爲0.6〜2.5當量,更好爲〇.8〜2.0當量之範圍。分子 中具有2個以上環狀(硫)醚基之熱硬化性成分之調配量 未達0.6時’由於造成阻焊劑膜中羧基殘留,使耐熱性、 耐鹼性、電絕緣性等下降,因而較不佳。另一方面,當超 過2.5當量時’由於乾燥塗膜中殘留低分子量環狀(硫) 醚基,使塗膜強度等降低故較不佳。 另外’可較好使用之熱硬化成分列舉爲三聚氰胺衍生 物、苯并鳥糞胺衍生物等。例如,羥甲基三聚氰胺化合物 、羥甲基苯并鳥糞胺化合物、羥甲基甘醇脲化合物及羥甲 -25- 201207555 基脲化合物等。另外,烷氧基甲基化三聚氰胺化合物、烷 氧基甲基化苯并鳥糞胺化合物、烷氧基甲基化甘醇脲化合 物及烷氧基甲基化脲化合物係藉由將各別之羥甲基三聚氰 胺化合物、羥甲基苯并鳥糞胺化合物、羥甲基甘醇脲化合 物及羥甲基脲化合物之羥甲基轉化成烷氧基甲基而獲得。 該等烷氧基甲基之種類並無特別限制,可爲例如甲氧基甲 基、乙氧基甲基、丙氧基甲基、丁氧基甲基等。最好爲對 人體或環境優異之福馬林濃度在0.2 %以下之三聚氰胺衍生 物。 該等之市售品可列舉爲例如Cyrnel (註冊商標)300、 Cymel 301、Cymel 303、Cymel 370、Cymel 325、Cymel 3 27、Cymel 701、Cymel 266、Cymel 267、Cymel 238、 Cymel 114 1、Cymel 2 7 2、Cymel 2 0 2、Cymel 1156、 Cymel 1158、Cymel 1123、Cymel 1170、Cymel 1174、 Cymel UFR65、Cymel 3 00 (以上均爲三井 Cyanamide (股 )製造)、NIKALAC (註冊商標)Mx-750、NIKALAC Mx-032 、 NIKALAC Mx-270 、 NIKALAC Mx-280 、 NIKALAC Mx-290、NIKALAC Mx-706、NIKALAC Mx-708 ' NIKALAC Mx-40、NIKALAC Mx-3 1、NIKALAC Ms-1 1 、NIKALAC Mw-30、NIKALAC Mw-30HM、NIKALAC Mw-390、NIKALAC Mw-IOOLM、NIKALAC Mw-7 50LM ( 以上爲三和化學(股)製造)等。 上述熱硬化成份可單獨使用亦可併用兩種以上。 又,本發明之光硬化性熱硬化性樹脂組成物可添加一 -26- 201207555 分子中具有兩個以上之異氰酸酯基或經封端化異氰酸酯基 之化合物,以提高組成物之硬化性及所得硬化膜之強韌性 。該種一分子中具有兩個以上之異氰酸酯基或經封端化之 異氰酸酯基之化合物列舉爲一分子中具有兩個以上異氰酸 酯基之化合物,亦即聚異氰酸酯化合物,或一分子中具有 兩個以上之封端化異氰酸酯基之化合物,亦即經封端之異 氰酸酯化合物等。 前述聚異氰酸酯化合物係使用例如芳香族聚異氰酸酯 、脂肪族聚異氰酸酯或脂環式聚異氰酸酯。芳香族聚異氰 酸酯之具體例列舉爲4,4’-二苯基甲烷二異氰酸酯、2,4-甲 苯二異氰酸酯、2,6-甲苯二異氰酸酯、萘-1,5-二異氰酸酯 、鄰-二甲苯二異氰酸酯、間-二甲苯二異氰酸酯及2,4-甲 苯二聚物。脂肪族聚異氰酸酯之具體例列舉爲四伸甲基二 異氰酸酯、六伸甲基二異氰酸酯、伸甲基二異氰酸酯、三 甲基六伸甲基二異氰酸酯、4,4-伸甲基雙(環己基異氰酸 酯)及異佛爾酮二異氰酸酯。脂環式聚異氰酸酯之具體例 列舉爲雙環庚烷三異氰酸酯。以及先前列舉之異氰酸酯化 合物之加成物、縮二脲體及異氰尿酸酯體》 封端異氰酸酯化合物中所含之封端化異氰酸酯基爲藉 由使異氰酸酯基與封端劑反應而受保護之暫時惰性化之基 。加熱至特定溫度時,該封端劑解離而生成異氰酸酯基。 經封端異氰酸酯化合物係使用異氰酸酯化合物與異氰 酸酯封端劑之加成反應產物。與封端劑反應所得之異氰酸 酯化合物列舉爲異氰尿酸酯型、縮二脲型、加成物型等。 -27- 201207555 該異氰酸酯化合物可使用例如芳香族聚異氰酸酯、脂肪族 聚異氰酸酯或脂環式聚異氰酸酯。芳香族聚異氰酸酯、脂 肪族聚異氰酸酯、脂環式聚異氰酸酯之具體例列舉爲如先 前例示之化合物。 異氰酸酯封端劑列舉爲例如酚、甲酚、二甲酚、氯酚 及乙基酚等酚系封端劑;ε-己內醯胺、δ-戊內醯胺、γ-丁 內醯胺及Ρ-丙內醯胺等內醯胺系封端劑;乙醯乙酸酯及乙 醯基丙酮等惰性伸甲基系封端劑;甲醇、乙醇、丙醇、丁 醇、戊醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單 丁基醚、二乙二醇單甲基醚、丙二醇單甲基醚、苄基醚、 乙醇酸甲酯、乙醇酸丁酯、二丙酮醇、乳酸甲酯及乳酸乙 酯等醇系封端劑;甲醛肟、乙醛肟、丙酮肟、甲基乙基酮 肟、二乙醯基單肟、環己烷肟等肟系封端劑;丁基硫醇、 己基硫醇、第三丁基硫醇、苯硫酚、甲基苯硫酚、乙基苯 硫酚等硫醇系封端劑;乙醯胺、苯甲醯胺等醯胺系封端劑 :琥珀醯亞胺及馬來醯亞胺等醯亞胺系封端劑;二甲苯胺 、苯胺、丁基胺、二丁基胺等胺系封端劑;咪唑、2-乙基 咪唑等咪唑系封端劑;伸甲基亞胺及伸丙基亞胺等亞胺系 封端劑等。 經封端之異氰酸酯化合物可爲市售者,列舉爲例如 Sumidur (註冊商標)BL-3175、BL-4165、BL-1100、BL-1265 , Desmodur (註冊商標)TPLS-2957 、 TPLS-2062 、 TPLS-2078、TPLS-2117,Desmotherm 2170 ' Desmotherm 2265 (以上爲住友Bayer Urethane公司製造,商品名)、 -28- 201207555(wherein, X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having a carbon number, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms) , an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, An amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and Y and Z each independently represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 to 8. Alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, an amine group, alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or a dialkylamino group substituted), a naphthyl group (an alkyl group having a carbon number of 1 to 17, an alkoxy group having a carbon number of 1 to 8, an amine group, and a hospital base having a carbon number of 1 to 8) Or a hospital amine-substituted), fluorenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond, or an alkyl group having a carbon number of 1 to 1, an alkyl group, a phenyl group , biphenyl, exopyridyl, anthranyl, thienyl, thiol, thiophene-15-201207555, furanyl, 2,5-pyridyl Ordole-diyl, 4,4,-stilbene diyl, 4,2'-styrenediyl, η is an integer of 0 or 1. In particular, in the above formula, X and oxime are respectively methyl or ethyl, hydrazine is methyl or phenyl, and η is O'Ar is preferably a bond, or a phenyl group, a naphthyl group, a thiophene group or a stretching group. Thienyl. The amount of the vinegar-based photopolymerization initiator to be added is preferably from 1 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When it is less than 1 part by mass, the photocurability is insufficient, and the film properties such as peeling of the coating film and chemical resistance are lowered. On the other hand, when it exceeds 5 parts by mass, the light absorption on the surface of the coating film becomes strong, and the deep hardenability tends to decrease. More preferably 0.5 to 3 parts by mass. The α-aminoacetophenone photopolymerization initiator is specifically exemplified as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-benzyl -2-dimethylamino-1-(4-morpholinylphenyl)-propan-1·one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]- 1·[4-(4-Morpholinyl)phenyl]-1-butanone, anthracene, fluorenyl-dimethylaminoacetophenone and the like. Commercially available products are Irgacure 907, Irgacure 3 69, Irgacure 3 79 manufactured by Ciba Corporation of Japan. The mercaptophosphorus oxide photopolymerization initiator is specifically exemplified as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzamide) Phenylphosphine oxide, bis(2,6-dimethoxybenzhydryl)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products are LUCILIN TPO manufactured by BASF Corporation, Irgacure 819 manufactured by Ciba Corporation, etc., etc., such α-aminoacetophenone photopolymerization initiator, mercaptophosphorus oxide-16-201207555 photopolymerization The amount of the initiator to be added is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When it is less than 0.01 part by mass, the same photohardenability to copper is insufficient, and the coating film is peeled off, and the film properties such as chemical resistance are lowered. On the other hand, when it exceeds 15 parts by mass, the effect of reducing the gas release cannot be obtained, and the light absorption on the surface of the coating film is enhanced, and the deep hardenability tends to be lowered. More preferably, it is 0.5 to 10 parts by mass, and a photopolymerization initiator, or a photoinitiator and a sensitizer which can be used for the resin composition of the present invention are exemplified by a benzoin compound and a phenyl group. A ketone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, a tertiary amine compound, and a xanthone compound. The benzoin compound is specifically exemplified by, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like. The acetophenone compound is specifically exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-Dichloroacetophenone and the like. The hydrazine compound is specifically exemplified by, for example, 2-methylhydrazine, 2-ethylhydrazine, 2-tert-butylphosphonium, 1-chloroindole or the like. The thioxanthone compound is specifically exemplified by, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone. Wait. Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like. The benzophenone compound is specifically exemplified by, for example, benzophenone, 4-phenyl-17-201207555 formazan diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-benzylidene-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenylsulfate, and the like. The tertiary amine compound is specifically exemplified by, for example, an ethanolamine compound or a compound having a dialkylaminobenzene structure. For example, a commercially available product is exemplified by 4,4 '-dimethylaminobenzophenone (manufactured by Nippon Soda Co., Ltd.). NISSOKUA MABP), 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), etc. Dialkylaminobenzophenone, 7-(diethylamino)-4 Methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) and other dialkylamine-containing coumarin compounds, 4-dimethyl Ethyl benzoate (KAYAKUA (registered trademark) EPA manufactured by Sakamoto Chemical Co., Ltd.), 2-dimethylaminobenzoic acid ethyl ester (Quantacure DMB manufactured by International Biosynthesis Co., Ltd.), 4-dimethylamino group Benzoic acid (n-butoxy)ethyl ester (Quantacure BEA manufactured by International Biosynthesis Co., Ltd.), p-dimethylaminobenzoic acid isoamyl ethyl ester (KAYAKUA-DMBI manufactured by Nippon Kayaku Co., Ltd.), 4-dimethyl 2-ethylhexyl benzoate (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), and the like. Among these, a thioxanthone compound and a tertiary amine compound are preferred. In particular, if it contains a thioxanthone compound, it is preferably in terms of deep hardenability, and preferably contains 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthene A thioxanthone compound such as a ketone or a 2,4-diisopropylthioxanthone. The compounding amount of the thioxanthone compound is preferably 20 parts by mass or less with respect to 100 parts by mass of the carboxylic acid-containing resin. When the amount of the thioxanthone compound is adjusted to -18-201207555, the film thickness is more than 20 parts by mass. The hardenability is reduced and is associated with an increase in the cost of the product. More preferably, it is 10 parts by mass or less. As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferred, and a dialkylaminobenzophenone compound is preferred, and a dialkylamine group having a maximum absorption wavelength of 350 to 450 nm is contained. a coumarin compound and a keto coumarin. As for the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because of low toxicity. The coumarin compound containing a dialkylamine group has a maximum absorption wavelength of 3 50 to 410 nm and an ultraviolet range, so that the coloring is small, and the coloring pigment is used to reflect the coloring pigment itself. The color of the film. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred. The amount of the tertiary amine compound to be added is preferably 0.1 to 20 parts by mass based on 1 part by mass of the carboxyl group-containing resin. When the amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that a sufficient sensitizing effect cannot be obtained. When it exceeds 20 parts by mass, the deep hardenability tends to decrease. More preferably, it is 0.1 to 10 parts by mass. These photopolymerization initiators, photoinitiating aids and sensitizers may be used singly or in combination of two or more. The total amount of the photopolymerization initiator, the photoinitiator, and the sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep hardening property tends to decrease due to the light absorption. Further, since the photopolymerization initiator, the photoinitiator, and the sensitizer have a specific wavelength due to absorption of -19-201207555, the sensitivity is lowered in some cases, and it acts as an ultraviolet absorber. However, these are not intended to enhance the sensitivity of the composition to the user. The light of a specific wavelength can be absorbed as needed to increase the photoreactivity of the surface, and the line shape and opening of the coating film become vertical, pyramidal, and chamfered, and the processing precision of the line width and the opening diameter is improved. The photopolymerization initiator is preferably an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a sulfhydryl phosphorus oxide photopolymerization initiator. One or more photopolymerization initiators selected from the group consisting of agents. Since the phthalic ester-based photopolymerization initiator has a good efficiency of the initiator, a small amount can effectively improve the sensitivity, so that after the formation of the photoresist film, it is known that the contamination or the volatilization due to the gas release during the heat treatment is small, and the film is effectively reduced. The warpage is preferred. Further, a tonoketone-based or coumarin-based sensitizer is preferable because it is effective in adjusting the cross-sectional shape of the resist. It is best to use both. The naphthalene ring-containing epoxy resin used in the photocurable thermosetting resin composition of the present invention can obtain a high heat-resistant coating film which is highly resistant to heat, in addition to the good overall reactivity of the prior art, and the resulting hardening. The coefficient of thermal expansion of the coating film (hereinafter referred to as CTE) does not decrease, and it is extremely effective for stress relaxation at the time of hardening of the solder resist. The naphthalene ring-containing epoxy resin is exemplified by, for example, HP-403 2 (manufactured by DIC), ΗΡ-4700 (manufactured by DIC), ESN-3 55 (manufactured by Tohto Kasei Co., Ltd.), and ESN-3. 75 (made by Toho Chemical Co., Ltd.), NC-73 00 (manufactured by Nippon Chemical Co., Ltd.). The most suitable ones are polyfunctional epoxy resins or derivatives thereof having a naphthalene ring skeleton and an aralkyl structure. The blending amount of the epoxy resin containing a naphthalene ring is preferably 5 parts by mass to 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the above-mentioned carboxyl group-containing -20-201207555 resin. When the amount of the epoxy resin containing a naphthalene ring is less than 5 parts by mass, the effect of the coating film is deteriorated, and the photoconductivity of the coating film is deteriorated, which may cause an image defect. Further, the photocurable thermosetting resin composition of the present invention may be added with a thermosetting component to impart heat resistance. The thermosetting component used in the present invention may be a protected isocyanate compound, an amine resin, a maleimide compound, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, or a polyfunctional ring. A thermosetting resin which is conventionally used, such as an oxygen compound, a polyfunctional oxetane compound, an episulfide resin, and a melamine derivative. The above-mentioned preferable thermosetting component is a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups (hereinafter simply referred to as cyclic (thio)ether groups) in one molecule. These thermosetting components having a cyclic (thio)ether group are commercially available in a wide variety of types, and various characteristics can be imparted depending on the structure. The thermosetting component having two or more cyclic (thio)ether groups in the molecule is any one of two or more three, four or five membered cyclic ether groups or cyclic thioether groups in the molecule. Or a compound of two kinds, for example, a compound having at least two or more epoxy groups in the molecule, that is, a compound having at least two or more oxetanyl groups in the molecule of the polyfunctional epoxy compound, that is, A functional oxetane compound, a compound having two or more thioether groups in its molecule, that is, an episulfide resin. As the polyfunctional epoxy compound, for example, jER (registered trademark) 828, jER834, jER1001 - 21 - 201207555, jER 1004 manufactured by Nippon Epoxy Co., Ltd., Epiclon (registered trademark) 840, Epiclon 850 manufactured by DIC Corporation are listed. Epiclon 1050, Epiclon 2055, EPOTOT (registered trademark) YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331, DER661, DER664 manufactured by Dao Chemical Co., Ltd. Japan's Ciba's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260' Sumitomo Chemical Industries, Inc. Sumi-epoxy ESA-011, ESA-014, E LA-115, ELA-128, AER330 manufactured by Asahi Kasei Industrial Co., Ltd. , AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; JERYL 903 manufactured by Japan Epoxy Resin Co., Ltd., Epiclon 152, Epiclon 165 manufactured by DIC Corporation, manufactured by Dongdu Chemical Co., Ltd. EPOTOT YDB-400, YDB-5 00 - DER542 manufactured by Dao Chemical Co., Ltd., Araldide 8011 from Ciba, Sumi-epoxy ESB-400, ESB-7 manufactured by Sumitomo Chemical Co., Ltd. 00, brominated epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd. VIII.11.711, VIII.£.11.714 (both trade names); jER 152, jER 154 manufactured by Japan Epoxy Resin Co., Ltd., manufactured by Dao Chemical Co., Ltd. DEN431, DEN438, Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by DIC, EPOTOT YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., Araldide ECN 1 23 manufactured by Sakamoto Ciba 5. Araldide ECN 1 273, Araldide ECN1299, Araldide XPY307, EPPN (registered trademark) 011, EOCN (registered trademark) - 1 025, EOCN-1020, EOCN-104S > RE-306, manufactured by Nippon Kayaku Co., Ltd., Sumitomo Sumi-epoxy ESCN-195X, ESCN-220, manufactured by Chemical Industry Co., Ltd., AOC ECN-235, ECN-299, etc. JER807 manufactured by Epiclon 830' Japan Epoxy Resin Co., Ltd., EPOTO YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd., Araldide XPY306 manufactured by Japan Ciba (both are trade names) Phenol F epoxy Lithium; hydrogenated bisphenol A type epoxy resin manufactured by Dongdu Chemical Co., Ltd., EPOTOT ST-2004, ST-2007, ST-3 000 (trade name); jER604 manufactured by Japan Epoxy Resin Co., Ltd., EPOTOT manufactured by Dongdu Chemical Co., Ltd. YH-434, Araldide MY720 manufactured by Sakamoto Ciba, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all trade names), glycidylamine epoxy resin; Araldide CY manufactured by Ciba Corporation of Japan -3 5 0 (trade name), etc., uranyl-type epoxy resin; Celloxide (registered trademark) 202 manufactured by Dicel Chemical Industry Co., Ltd. 1, Araldide CY 175 'CY 179 manufactured by Ciba Corporation, etc. Aliphatic epoxy resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., TEN·, ΕΡΡΝ·501, ΕΡΡΝ-502, etc. (all trade names) manufactured by Dao Chemical Co., Ltd. Epoxy resin; bis-xylenol type or biphenol type epoxy resin such as YL-605 6 , ΥΧ-4000, YL-6121 (both trade names) manufactured by Japan Epoxy Resin Co., Ltd. or a mixture thereof; Japan EBPS-200, ADEK manufactured by Chemical Pharmaceutical Co., Ltd. A30 manufactured by Company A, bisphenol δ type epoxy resin such as ΕΧΑ-1514 (trade name) manufactured by DIC Corporation; bisphenol a phthalic acid varnish epoxy resin such as jER157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Resin; jERYL-931 manufactured by Japan Epoxy Resin Co., Ltd., Araldide 163 manufactured by Japan Automobile Enterprise Co., Ltd. (all trade names), tetraphenyl-23-201207555 mercaptoethane type epoxy resin; manufactured by Japan Ciba Araldide PT810 (trade name), a heterocyclic epoxy resin of TEPIC (registered trademark) manufactured by Nissan Chemical Industries Co., Ltd.; diglycidyl acrylate resin such as Blenmer (registered trademark) DGT manufactured by Nippon Oil & Fats Co., Ltd.: Dongdu Tetraglycidyl xylene decyl ethane resin such as ZX-1 063 manufactured by Kasei Co., Ltd.; ESN-190, ESN-3 60 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA manufactured by DIC Corporation -4700 epoxy resin containing naphthyl group; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; glycidol such as CP-50S and CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Methyl methacrylate copolymerization Epoxy resin; further, copolymerized epoxy resin of cyclohexylmalamine and glycidyl methacrylate; epoxy modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Dicel Chemical Industry Co., Ltd.) ), CTBN modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd.), etc., but is not limited thereto. These epoxy resins may be used singly or in combination of two or more. In particular, the novolac type epoxy resin, the modified novolac type epoxy resin, the heterocyclic epoxy resin, the bisphenol type epoxy resin or a mixture thereof is preferably the aforementioned polyfunctional oxygen heterocycle. The butane compound is exemplified by bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether' 1 , 4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene , (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3-methyl-3-oxo- 24 - 201207555 Heterocyclic butyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxetane such as oligomers or copolymers thereof And oxetane and novolak resins, poly(p-hydroxystyrene), CALDO type bisphenols, calixarene, resorcinol calixarenes (calixresorcinarene), or sesquiterpene oxide, etc. An etherified product of a resin having a hydroxyl group or the like. Further, it is exemplified by a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate. The episulfide compound having two or more cyclic (thio)ether groups in the above molecule is exemplified by, for example, YL7000 (bisphenol A type episulfide resin) manufactured by Nippon Epoxy Resin Co., Ltd., or YSLV manufactured by Toshiro Kasei Co., Ltd. -120TE and so on. Further, an episulfide resin such as an oxygen atom of an epoxy group of a novolac type epoxy resin may be replaced by a sulfur atom by the same synthesis method. The compounding ratio of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is preferably from 0.6 to 2.5 equivalents, more preferably from 0.8 to 2.5 equivalents, per mole of the carboxyl group of the carboxyl group-containing resin. A range of 2.0 equivalents. When the amount of the thermosetting component having two or more cyclic (thio)ether groups in the molecule is less than 0.6, the heat resistance, alkali resistance, electrical insulation, and the like are lowered due to residual carboxyl groups in the solder resist film. Less good. On the other hand, when it exceeds 2.5 equivalents, it is less preferable because the low molecular weight cyclic (thio)ether group remains in the dried coating film to lower the strength of the coating film and the like. Further, the thermosetting component which can be preferably used is melamine derivative, benzoguanamine derivative or the like. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol-25-201207555-based urea compound. In addition, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycol urea compound, and the alkoxymethylated urea compound are each It is obtained by converting a methylolamine compound, a methylol benzoguanamine compound, a methylol glycol urea compound, and a methylol group of a methylol urea compound into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. It is preferably a melamine derivative having a formalin concentration of 0.2% or less which is excellent for the human body or the environment. Such commercially available products can be exemplified by, for example, Cyrnel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 3 27, Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 114 1, Cymel. 2 7 2. Cymel 2 0 2. Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 3 00 (all manufactured by Mitsui Cyanamide Co., Ltd.), NIKALAC (registered trademark) Mx-750 , NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALAC Mx-706, NIKALAC Mx-708 'NIKALAC Mx-40, NIKALAC Mx-3 1, NIKALAC Ms-1 1 , NIKALAC Mw -30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw-IOOLM, NIKALAC Mw-7 50LM (above is manufactured by Sanwa Chemical Co., Ltd.). The above-mentioned thermosetting component may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be added with a compound having two or more isocyanate groups or blocked isocyanate groups in the molecule of -26 to 201207555 to improve the hardenability of the composition and the resulting hardening. The toughness of the film. The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is exemplified as a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two or more in one molecule. A compound which blocks an isocyanate group, that is, a blocked isocyanate compound or the like. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate are 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene Diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate are tetramethylammonium diisocyanate, hexamethylene diisocyanate, methyl diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methyl bis(cyclohexyl). Isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate are biscycloheptane triisocyanate. And the previously listed isocyanate compound adduct, biuret and isocyanurate body. The blocked isocyanate group contained in the blocked isocyanate compound is protected by reacting the isocyanate group with the blocking agent. The basis for temporary inertization. Upon heating to a specific temperature, the blocking agent dissociates to form an isocyanate group. The blocked isocyanate compound is an addition reaction product of an isocyanate compound and an isocyanate blocking agent. The isocyanate compound obtained by the reaction with a blocking agent is exemplified by an isocyanurate type, a biuret type, an addition type, and the like. -27- 201207555 The isocyanate compound can be, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate are exemplified as the compounds exemplified above. The isocyanate blocking agent is exemplified by a phenolic terminal blocking agent such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroinamide, γ-butyrolactone and An internal amide-based blocking agent such as Ρ-propionalamine; an inert methyl-terminated blocking agent such as acetamidine acetate and acetonitrile; methanol, ethanol, propanol, butanol, pentanol, and ethylene Alcohol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate , alcohol-based terminal blocking agents such as diacetone alcohol, methyl lactate and ethyl lactate; oxime systems such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, cyclohexane hydrazine Blocking agent; thiol-based capping agent such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acetamidine, benzamidine Amidoxime-based blocking agent such as amine: a quinone imine blocking agent such as amber quinone and maleimine; an amine blocking agent such as xylidine, aniline, butylamine or dibutylamine; , imidazole seals such as 2-ethylimidazole The terminal agent; an imide-based blocking agent such as methylimine and propylimine. The blocked isocyanate compound is commercially available, and is exemplified by, for example, Sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS. -2078, TPLS-2117, Desmotherm 2170 'Desmotherm 2265 (above is Sumitomo Bayer Urethane, trade name), -28- 201207555
Coronate (註冊商標)2512 、 Coronate 2513 、 Coronate 2520 (以上爲日本p〇1yurethane工業公司製造’商品名) ,B- 8 3 0 ' B-815、B-846、B-870、B-874、B-882 (二井武 田化學公司製造’商品名)、TPA_B80E、17B-60PX、 E402-B80T (旭化成化學公司製造’商品名)等。又’ Sumiduf BL_3175、BL-4265爲使用甲基乙基肟作爲封端劑 獲得者。 上述一分子中具有兩個以上異氰酸酯基或封端化異氰 酸酯基之化合物可單獨使用一種或組合兩種以上使用。 該種一分子中具有兩個以上異氰1酸酯基或封端化異氰 酸酯基之化合物之調配量’相對於前述含有羧基之樹脂 100質量份,宜爲1~1〇〇質量份’較好爲2〜70質量份之比例 。前述調配量未達1質量份時’無法獲得充分之塗膜強韌 性,故而不佳當。另一方面,超過100質量份時’儲存安 定性下降故不佳。 本發明之光硬化性熱硬化性樹脂組成物中,可添加胺 基甲酸酯化觸媒以促進羥基或羧基與異氰酸酯基之硬化反 應。至於胺基甲酸酯化觸媒較好使用由錫系觸媒、金屬氯 化物、金屬乙醯基丙酮酸鹽、金屬硫酸鹽、胺化合物、或 /及胺鹽所組成群組選出之一種以上之胺基甲酸酯化觸媒 前述錫系觸媒列舉爲例如辛酸亞錫(stannous octoate )、二丁基錫二月桂酸酯等有機錫化合物、無機錫化合物 等。 -29- 201207555 前述金屬氯化物爲由Cr、Μη、Co、Ni、Fe、Cu或A1 所組成之金屬之氯化物,列舉爲例如氯化鈷、氯化亞鎳、 氯化鐵等。 前述金屬乙醯基丙酮酸鹽爲由Cr、Mn、Co、Ni、Fe 、Cu或A1所組成之金屬之乙醯基丙酮酸鹽,列舉爲例如乙 醯基丙酮酸鈷、乙醯基丙酮酸鎳、乙醯基丙酮酸鐵等。 前述金屬硫酸鹽爲由Cr、Mn、Co、Ni、Fe、Cu或A1 所組成之金屬之硫酸鹽,列舉爲例如硫酸銅等。 前述胺化合物列舉爲例如過去習知之三乙二胺、 N,N,N’,N’-四甲基-1,6-己二胺、雙(2-二甲胺基乙基)醚 、N,N,N’,N’’,N”-五甲基二伸乙基三胺、N-甲基嗎咐、N-乙基嗎啉、N,N-二甲基乙醇胺、二嗎啉基二乙基醚、N-甲 基咪唑、二甲胺基吡啶、三嗪、N ’ - ( 2 -羥基乙基)-N,N,N’-三甲基-雙(2-胺基乙基)醚、N,N-二甲基己醇胺 、>1,>1-二甲基胺基乙氧基乙醇、;^,:^,:^’-三甲基->^’-(2-羥 基乙基)伸乙二胺、N- ( 2-羥基乙基)-N,N’,N”,N”-四甲 基二伸乙三胺、N- ( 2-羥基丙基)-N,N’,N”,N”-四甲基二 伸乙三胺、Ν,Ν,Ν’-三甲基-Ν’- ( 2-羥基乙基)丙二胺、N-甲基-Ν’- ( 2-羥基乙基)哌啶、雙(Ν,Ν-二甲基胺基丙基 )胺、雙(Ν,Ν-二甲基胺基丙基)異丙醇胺、2-胺基喹寧 環(quinuclidine) 、3-胺基喹寧環、4-胺基喹寧環、2-喹 寧環二醇、3-喹寧環二醇、4-喹寧環二醇、1- (2’-羥基丙 基)咪唑、1- (2’-羥基丙基)-2-甲基咪唑、1- (2’-羥基 乙基)咪唑、1-(2’-羥基乙基)-2-甲基咪唑、1-(2’-羥 -30- 201207555 基丙基)-2 -甲基咪唑、1-(3胺基丙基)咪唑、1-(3,-胺基丙基)-2 -甲基咪唑、1- (3,-羥基丙基)咪唑、1-( 3羥基丙基)-2-甲基咪唑、N,N-二甲基胺基丙基-Ν’- (2-羥基乙基)胺' Ν,Ν-二甲基胺基丙基-Ν’,Ν’-雙(2-羥基乙 基)胺、Ν,Ν-二甲基胺基丙基-Ν’,Ν’-雙(2-羥基丙基)胺 、:Ν,Ν-二甲基胺基乙基-Ν’,Ν’-雙(2-羥基乙基)胺、Ν,Ν-二甲基胺基乙基-Ν’,Ν’-雙(2-羥基丙基)胺、三聚氰胺及 /或苯并鳥糞胺等。 前述胺鹽列舉爲例如DBU ( 1,8-二氮雜-雙環[5,4,0]十 一碳烯-7)之有機酸鹽系之胺鹽等。 前述胺基甲酸酯化觸媒之調配量以通常量之比例即已 足夠,例如相對於含有羧基之樹脂(A ) 1 00質量份,較好 爲0.1〜20質量份,更好爲0.5~10.0質量份。 使用上述分子中具有兩個以上之環狀(硫)醚基之熱 硬化性成分時,較好含有熱硬化觸媒。該等熱硬化觸媒列 舉爲例如咪唑、2-甲基咪唑' 2-乙基咪唑、2-乙基-4-甲基 咪唑、2-苯基咪唑、4-苯基咪唑、1-氰基乙基-2·苯基咪唑 、1-(2-氰基乙基)-2-乙基-4-甲基咪唑等之唑衍生物; 二氰基二醯胺、苄基二甲基胺、4_(二甲胺基)·Ν,Ν_二 甲基苄基胺、4-甲氧基-Ν,Ν-二甲基苄基胺、4-甲基-Ν,Ν-二甲基苄基胺等胺化合物,己二酸二醯肼、癸二酸二醯肼 等醯肼化合物;三苯基膦等磷化合物等。另外市售者列舉 爲例如四國化成工業公司製造之2ΜΖ-Α、2ΜΖ-ΟΚ、2ΡΗΖ 、2Ρ4ΒΗΖ、2Ρ4ΜΗΖ (均爲咪唑系化合物之商品名)' -31 - 201207555 SAN-APRO公司製造之U-CAT (註冊商標)3503N、U-CAT 3502T (均爲二甲基胺之嵌段異氰酸酯化合物之商品名) 、DBU、DBN、U-CATSA102、U-CAT5002 (均爲二環式脒 化合物及其鹽)等。尤其,並不限定於該等,若是環氧樹 脂及氧雜環丁烷化合物之熱硬化觸媒,或是促進環氧基及 /或氧雜環丁烷基與羧基之反應,則單獨使用或混合兩種 以上使用均無妨。又,可使用鳥糞胺、乙醯基鳥糞胺、苯 并鳥糞胺、三聚氰胺、2,4-二胺基-6-甲基丙烯醯基氧基乙 基-S-三嗪、2-乙烯基-2,4-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪•異氛尿酸加成物、2,4-二胺基-6-甲基丙 烯醯氧基乙基-S-三嗪.異氰尿酸加成物等之S-三嗪衍生物 ’較好亦將該等作爲密著性賦予劑功能之化合物與上述熱 硬化性觸媒倂用》 該等熱硬化性觸媒之調配量,以通常量之比例即已足 夠’例如相對於含有羧酸之樹脂或分子中具有兩個以上之 環狀(硫)醚基之熱硬化性成分100質量份,較好爲 0.1〜20質量份,更好爲0.5~15.0質量份。 本發明之光硬化性樹脂組成物可調配著色劑。至於著 色劑亦可使用紅、藍、綠、黃等慣用之習知著色劑 '顏料 '染料、色素之任一種。具體而言列舉附有如下述之色彩 係數(C.I·,染料及色彩協會(The Society of Dyers and Colourists )發行)編號者。但,就降低環境負荷及對人 體影響之觀點而言,較好不含鹵素。 -32- 201207555 紅色著色劑: 紅色著色劑有單偶氮系、二偶氮系、可溶性偶氮染料 系、苯并咪唑酮系、茈系、二酮吡咯并吡咯系、縮合偶氮 系、蒽醌系、喹吖啶酮系等,具體而言可列舉爲附有如下 述之色彩係數(C.I·,染料及色彩協會(The Society ofCoronate (registered trademark) 2512, Coronate 2513, Coronate 2520 (above is manufactured by Japan p〇1yurethane Industrial Co., Ltd.), B- 8 3 0 'B-815, B-846, B-870, B-874, B -882 (manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA_B80E, 17B-60PX, E402-B80T (product name manufactured by Asahi Kasei Chemicals Co., Ltd.). Further, 'Sumiduf BL_3175 and BL-4265 are those obtained using methyl ethyl hydrazine as a terminal blocking agent. The compound having two or more isocyanate groups or blocked isocyanate groups in the above molecule may be used alone or in combination of two or more. The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably from 1 to 1 part by mass based on 100 parts by mass of the carboxyl group-containing resin. It is a ratio of 2 to 70 parts by mass. When the amount of the above formulation is less than 1 part by mass, sufficient coating film toughness cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable. In the photocurable thermosetting resin composition of the present invention, a urethanization catalyst may be added to promote a hardening reaction of a hydroxyl group or a carboxyl group with an isocyanate group. As the urethane-based catalyst, one or more selected from the group consisting of a tin-based catalyst, a metal chloride, a metal acetylacetonate, a metal sulfate, an amine compound, or an amine salt is preferably used. The urethane-based catalyst The tin-based catalyst is exemplified by an organic tin compound such as stannous octoate or dibutyltin dilaurate, or an inorganic tin compound. -29- 201207555 The metal chloride is a chloride of a metal composed of Cr, Μη, Co, Ni, Fe, Cu or A1, and is exemplified by cobalt chloride, nickel chloride, iron chloride and the like. The aforementioned metal ethyl pyruvate is an ethyl phthalate pyruvate of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or A1, and is exemplified by, for example, cobalt acetylacetonate and acetylpyruvate. Nickel, iron acetylacetonate and the like. The metal sulfate is a sulfate of a metal composed of Cr, Mn, Co, Ni, Fe, Cu or A1, and is exemplified by, for example, copper sulfate. The aforementioned amine compound is exemplified by, for example, conventionally used triethylenediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, bis(2-dimethylaminoethyl)ether, N ,N,N',N'',N"-pentamethyldiethylideneamine, N-methyloxime, N-ethylmorpholine, N,N-dimethylethanolamine, dimorpholinyl Diethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'-(2-hydroxyethyl)-N,N,N'-trimethyl-bis(2-aminoethyl Ether, N,N-dimethylhexanolamine, >1,>1-dimethylaminoethoxyethanol, ;^,:^,:^'-trimethyl->^' -(2-hydroxyethyl) ethylenediamine, N-(2-hydroxyethyl)-N,N',N",N"-tetramethyldiethylenetriamine, N-(2-hydroxypropane ))-N,N',N",N"-tetramethyldiethylenetriamine, hydrazine, hydrazine, Ν'-trimethyl-Ν'-(2-hydroxyethyl)propanediamine, N- Methyl-Ν'-(2-hydroxyethyl)piperidine, bis(indole, Ν-dimethylaminopropyl)amine, bis(indole, Ν-dimethylaminopropyl)isopropanolamine , 2-aminoquinine ring (quinuclidine), 3-aminoquinine ring, 4-aminoquinine ring 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1-(2'-hydroxypropyl)imidazole, 1-(2'-hydroxypropyl)-2-methyl Imidazole, 1-(2'-hydroxyethyl)imidazole, 1-(2'-hydroxyethyl)-2-methylimidazole, 1-(2'-hydroxy-30- 201207555-propyl)-2 Methylimidazole, 1-(3aminopropyl)imidazole, 1-(3,-aminopropyl)-2-methylimidazole, 1-(3,-hydroxypropyl)imidazole, 1-(3hydroxyl) Propyl)-2-methylimidazole, N,N-dimethylaminopropyl-Ν'-(2-hydroxyethyl)amine 'Ν, Ν-dimethylaminopropyl-Ν', Ν '-Bis(2-hydroxyethyl)amine, hydrazine, hydrazine-dimethylaminopropyl-hydrazine, Ν'-bis(2-hydroxypropyl)amine, hydrazine, hydrazine-dimethylamino Ethyl-hydrazone, Ν'-bis(2-hydroxyethyl)amine, hydrazine, hydrazine-dimethylaminoethyl-hydrazine, Ν'-bis(2-hydroxypropyl)amine, melamine and/or Or benzoguanamine or the like. The amine salt is exemplified by an amine salt of an organic acid salt such as DBU (1,8-diaza-bicyclo[5,4,0]undecene-7). It is sufficient that the amount of the urethane catalyst is adjusted in a usual amount. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the resin (A) containing a carboxyl group. The above molecule has two or more cyclic (thio)ether groups. In the case of a thermosetting component, it is preferred to contain a thermosetting catalyst. Examples of such thermosetting catalysts are, for example, imidazole, 2-methylimidazole '2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- An azole derivative such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Dicyanodiamine, benzyldimethylamine, 4-(dimethylamino) hydrazine, hydrazine-dimethylbenzylamine, 4-methoxy-hydrazine, hydrazine-dimethylbenzylamine, An amine compound such as 4-methyl-hydrazine or hydrazine-dimethylbenzylamine; an anthracene compound such as diammonium adipate or diterpene sebacate; or a phosphorus compound such as triphenylphosphine. In addition, the market name is, for example, 2ΜΖ-Α, 2ΜΖ-ΟΚ, 2ΡΗΖ, 2Ρ4ΒΗΖ, 2Ρ4ΜΗΖ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd.' -31 - 201207555 U-Manufactured by SAN-APRO CAT (registered trademark) 3503N, U-CAT 3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic guanidine compounds and their salts) )Wait. In particular, it is not limited to these, and if it is a thermosetting catalyst of an epoxy resin and an oxetane compound, or a reaction promoting an epoxy group and/or an oxetane group and a carboxyl group, it is used alone or Mixing two or more uses is fine. Further, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2- Vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine • isophthalic acid adduct, 2,4-diamino-6 - an S-triazine derivative such as a methacryloxyethyl-S-triazine or an isocyanuric acid adduct, and a compound which functions as an adhesion imparting agent and the above-mentioned thermosetting property Catalyst use" The amount of these thermosetting catalysts is sufficient in the proportion of the usual amount, for example, relative to the heat of the carboxylic acid-containing resin or the molecule having two or more cyclic (thio)ether groups. The curable component is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass. The photocurable resin composition of the present invention can be formulated with a colorant. As the coloring agent, any of the conventional coloring agents 'pigment' dyes and pigments such as red, blue, green, and yellow may be used. Specifically, the number of the color coefficient (C.I., issued by The Society of Dyers and Colourists) is attached. However, in terms of reducing environmental load and affecting human body, it is preferred that halogen is not contained. -32- 201207555 Red coloring agent: Red coloring agent is monoazo, diazo, soluble azo dye, benzimidazolone, lanthanide, diketopyrrolopyrrole, condensed azo, hydrazine Anthraquinone, quinacridone, etc., specifically, may be exemplified by a color coefficient (CI·, Dyes and Color Association (The Society of
Dyers and Colourists)發行)編號者。 單偶氮系:顏料紅 1、2、3、4、5、6、8、9、12、14 、15、 16、 17、 21、 22、 23、 31、 32、 112、 114、 146、 147、 151、 170、 184、 187、 188、 193、 210、 245、 253、 258 ' 266 、 267 、 268 、 269 。 二偶氮系:顏料紅37、38、41。 可溶性單偶氮染料系:顏料紅48:1、48:2、48:3、 48:4 、 49:1 、 49:2 、 50:1 、 52:1 、 52:2 、 53:1 、 53:2 、 57:1 、58:4、 63:1 ' 63:2、 64:1、 68。 苯并咪唑酮系:顏料紅171、顏料紅175、顏料紅176 、顏料紅185、顔料紅208。 茈系:溶劑紅135、溶劑紅179、顏料紅123、顏料紅 149、顏料紅166、顏料紅178、顔料紅179、顏料紅190、 顏料紅194、顏料紅224。 二酮吡咯并吡咯系:顏料紅254、顏料紅25 5、顏料紅 2 64、顏料紅270、顏料紅272。 縮合偶氮系:顏料紅220、顏料紅144、顏料紅166、 顏料紅2 1 4、顏料紅2 2 0、顏料紅2 2 1、顏料紅2 4 2。 蒽醌系:顔料紅168、顏料紅177、顔料紅216、顏料 -33- 201207555 紅1 4 9、顏料紅1 5 0、溶劑紅5 2、溶劑紅2 0 7。 喹吖啶酮系:顔料紅122、顏料紅202、顏料紅206、 顏料紅207、顏料紅209。 藍色著色劑: 藍色著色劑有酞花菁系、蒽醌系,顔料系係分類爲顏 料(Pigment )之化合物,具體而言可列舉爲下述者:顏 料藍15、顏料藍15:1、顏料藍15:2、顏料藍15:3、顏料藍 15:4、顏料藍15:6、顔料藍16、顏料藍60。 染料系可使用溶劑藍35、溶劑藍63、溶劑藍68、溶劑 藍70、溶劑藍83、溶劑藍87、溶劑藍94、溶劑藍97、溶劑 藍122、溶劑藍136、溶劑藍67、溶劑藍70等。除上述外, 亦可使用經金屬取代或未經取代之酞花菁化合物。 綠色著色劑: 綠色著色劑同樣有酞花菁系、蒽醌系,茈系。具體而 言可使用顏料綠7、顏料綠3 6、溶劑綠3、溶劑綠5、溶劑 綠2 0、溶劑綠2 8等。除上述外’亦可使用經金屬取代或未 經取代之酞花脊化合物。 黃色著色劑: 黃色著色劑爲單偶氮系二偶氮系、縮合偶氮系、苯 并咪唑酮系、異吲哚酮系、蒽醌系等,具體而言列舉爲下 列者。 -34- 201207555 惠醒系:溶劑黃163、顏料黃24、顔料黃1〇8、顏料黃 M3、顏料黃147、顏料黃199、_黃2〇^ / 異吲哚酮系·顏料黃110、顏料黃109、顔料黃139、 顔料黃179、顏料黃185。 縮合偶氮系:顏料黃93、 顏料黃94、顏料黃95、顏料 黃128、顔料黃155、顔料黃166、顔料黃180。 本并咪唑酮系:顔料黃12〇、顏料黃151、顏料黃I54 、顏料黃156、顔料黃175、顏料黃181。 單偶氮系:顏料黃 1、2、3、4、5、6、9、1()、12、 61、62、62:1、65、73、74、75、97、100、1〇4、105、 111、 116、 167、 168、 169、 182、 183。 —偶氮系:顏料黃 12、13、14、16、17、55、63、81 ' 83、 87、 126、 127、 152' 170、 172、 174、 176、 188、 198° 另外,爲了調整色調,亦可添加紫色、橙色、茶色、 黑色等著色劑。 具體之例示爲顏料紫19、23、29、32、36、38、42、 溶劑紫13、36、C.I.顏料橙1、C.I.顏料橙5、C.I.顏料橙13 、C.I.顏料橙14、C.I·顏料橙16' C.I.顔料橙17、C.I.顏料 橙24、C.I.顏料橙34、C.I.顔料橙36、C.I.顏料橙38、C.I. 顔料橙40、C.I.顏料橙43、C.I.顏料橙46、C.I.顔料橙49、 C.I.顏料橙51、C_I.顏料橙61、C.I.顏料橙63、C.I.顏料橙 64、C.I.顏料橙71、C.I.顏料橙73、C.I.顏料棕23、C.I·顏 料棕25、C.I.顏料黑1、C.I.顏料黑7等。 -35- 201207555 前述著色劑之調配比例並無特別限制,但相對於 含羧基之樹脂100質量份,較好爲0〜10質量份,最 0.1 ~ 5質量份之比例。 本發明之光硬化性熱硬化性樹脂組成物中使用之 中具有兩個以上之乙烯性不飽和基之化合物,係藉由 能量線之照射,經光硬化,使前述含有羧基之樹脂於 水溶液中不溶化,或有助於不溶化者。該等化合物可 慣用習知之聚酯(甲基)丙烯酸酯、聚醚(甲基)丙 酯、胺基甲酸酯(甲基)丙烯酸酯、碳酸酯(甲基) 酸酯、環氧(甲基)丙烯酸酯等。具體而言,列舉爲 丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基丙酯等丙烯酸 烷酯類;乙二醇、甲氧基四乙二醇、聚乙二醇、丙二 二醇之二丙烯酸酯類:N,N-二甲基丙烯醯胺、N-羥甲 烯醯胺、N,N-二甲基胺基丙基丙烯醯胺等丙烯醯胺 N,N-二甲基胺基乙基丙烯酸酯、N,N-二甲基胺基丙基 酸酯等丙烯酸胺基烷酯類:己二醇、三羥甲基丙烷、 四醇、二季戊四醇、三-羥基乙基異氰尿酸酯等多價 該等之環氧乙烷加成物、環氧丙烷加成物、或者ε-己 加成物等多價丙烯酸酯類;丙烯酸苯氧酯、雙酚Α二 酸酯、及該等酚類之環氧乙烷加成物或者環氧丙烷加 等多價丙烯酸酯類;甘油二縮水甘油醚、甘油三縮水 醚、三羥甲基丙烷三縮水甘油醚、三縮水甘油基異氰 酯等縮水甘油醚之多價丙烯酸酯類;不限於上述,而 例有使聚醚多元醇、聚碳酸酯二醇、羥基末端之聚丁 前述 好爲 分子 活性 鹼性 使用 烯酸 丙烯 甲基 羥基 醇等 基丙 類; 丙烯 季戊 醇或 內酯 丙烯 成物 甘油 尿酸 可舉 二烯 -36- 201207555 、聚酯多元醇等多元醇直接丙烯酸酯化,或者透過 酸酯經胺基甲酸酯丙烯酸酯化之丙烯酸酯類及三聚 烯酸酯,及/或對應於上述丙烯酸酯之各種甲基丙 類等。 再者,列舉有使甲酚酚醛清漆樹脂型環氧樹脂 能基環氧樹脂與丙烯酸反應之環氧基丙烯酸酯樹脂 而使其環氧基丙烯酸酯樹脂之羥基與季戊四醇三丙 等之羥基丙烯酸酯與異彿爾酮二異氰酸酯等之二異 之半胺基甲酸酯化合物反應而成之環氧基胺基甲酸 酸酯化合物等。該等環氧基丙基酸酯系樹脂不降低 燥性,而可提升光硬化性。 該等分子中具有2個以上乙烯性不飽和基之化 調配量,相對於前述含有羧基之樹脂100質量份, 5〜100質量份,更好爲1~70質量份之比例。當前述 未達5質量份時,光硬化性會降低,經活性能量線 藉由鹼顯像難以形成圖型,因而較不佳。另一方面 過1 〇〇質量份時,有對於鹼性水溶液之溶解性下降 變脆之傾向,因此較不佳。 本發明之光硬化性熱硬化性樹脂組成物,爲提 膜之物理強度,而可視需要調配塡充劑。該等塡充 用習知慣用之無機或有機塡充劑,但尤其較好使用 、球狀二氧化矽以及滑石》再者,亦可使用以氧化 屬氧化物、氫氧化鋁等金屬氫氧化物作爲體質顔料 ,以獲得白色外觀或難燃性。該等塡充劑之調配量 二異氰 氰胺丙 烯酸酯 等多官 ,及進 烯酸酯 氰酸酯 酯丙烯 指觸乾 合物之 較好爲 調配率 照射後 ,當超 ,塗膜 高其塗 劑可使 硫酸鋇 鈦或金 塡充劑 ,對於 -37- 201207555 目IJ述含有殘基之樹脂100質量份,較好爲200質量份以下, 更好爲0.1〜150質量份,最好爲1〜1〇〇質量份。於塡充劑之 調配率超過200質量份時’有組成物之黏度變高,使印刷 性降低,硬化物變脆之情況,故較不佳。 再者本發明之光硬化性熱硬化性樹脂組成物亦可使用 結合劑聚合物以改善指觸乾燥性、改善操作性等。可使用 例如聚酯系聚合物 '聚胺基甲酸酯系聚合物、聚酯胺基甲 酸酯系聚合物、聚胺基甲酸酯聚合物、聚酯胺基甲酸醋系 聚合物、聚醯胺系聚合物、聚酯醯胺系聚合物、丙烯酸系 聚合物、纖維素系聚合物、聚乳酸系聚合物、苯氧基系聚 合物等。該等結合劑聚合物可單獨使用或以兩種以上之混 合物使用。 另外本發明之光硬化性熱硬化性樹脂組成物可使用含 有羥基之彈性體或其他彈性體以賦予柔軟性、改善硬化物 之脆度等。可使用例如聚酯系彈性體、聚胺基甲酸酯系彈 性體、聚酯胺基甲酸酯系彈性體、聚醯胺系彈性體、聚酯 醯胺系彈性體、丙烯酸系彈性體、烯烴系彈性體。另外, 亦可使用使具有各種骨架之環氧樹脂之一部分或全部之環 氧基改質成爲兩末端羧酸改質型丁二烯-丙烯腈橡膠之樹 脂等。另外亦可使用含有環氧基之聚丁二烯系彈性體 '含 有丙烯酸之聚丁二烯系彈性體等。該等彈性體可單獨使用 或以兩種以上之混合物使用。 再者’本發明之光硬化性熱硬化性樹脂組成物,可使 用有機溶劑用於上述含有羧基之樹脂合成或組成物之調製 -38- 201207555 ,或用於調整塗佈於基板或承載膜上之黏度。 該等有機溶劑,可舉例爲酮類、芳香族烴類、二醇醚 類、二醇醚乙酸酯類、酯類、醇類、脂肪族烴類、石油系 溶劑等。更具體而言,爲甲基乙基酮、環己酮等之酮類; 甲苯、二甲苯、四甲基苯等之芳香族烴類;溶纖劑、甲基 溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇 、丙二醇單甲基醚、二丙二醇單甲基醚、二丙二醇二乙基 醚、三乙二醇單乙基醚等之二醇醚類;乙酸乙酯、乙酸丁 酯、二丙二醇甲基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二 醇乙基醚乙酸酯、丙二醇丁基醚乙酸酯等之酯類;乙醇、 丙醇、乙二醇、丙二醇等之醇類;辛烷、癸烷等之脂肪族 烴;石油醚、石油腦、氫化石油腦、溶劑石油腦等之石油 系溶劑。該等有機溶劑可單獨使用或以2種以上之混合物 使用。 —般而言,當高分子材料之大部分一旦開始氧化時, 會引起後續連鎖的氧化劣化,使高分子材料之功能下降, 故本發明之光硬化性熱硬化性樹脂組成物可添加用於防止 氧化之(1 )使產生之自由基無效化之自由基捕捉劑及/或 (2)將產生之過氧化物分解成無害物質,且不產生新的 自由基之過氧化物分解劑等抗氧化劑。 作爲自由基捕捉劑發揮作用之抗氧化劑之具體之化合 物列舉爲氫醌、4-第三丁基兒茶酚、2-第三丁基氫醌、氫 醌單甲基醚、2,6-二-第三丁基-對-甲酚、2,2-伸甲基-雙( 4-甲基-6-第三丁基酚)、1,1,3-參(2-甲基-4-羥基-5-第三 -39- 201207555 丁基苯基)丁烷、1,3,5-三甲基-2,4,6-參(3,5-二-第三丁 基-4-羥基苄基)苯、1,3,5-參(3’,5’-二-t-丁基-4-羥基苄 基)-3-三井-2,4,6-(11^,311,51〇三酮等酚系、焦掊酚、 苯醌等醌系化合物,雙(2,2,6,6-四甲基-4-哌啶基)-癸二 酸酯、吩噻嗪(Phenothiazin)等胺系化合物等。 自由基捕捉劑可爲市售者,列舉爲例如ADEKASTAB (註冊商標)AO-30 、 ADEKASTAB AO-3 3 0 、 ADEKASTAB AO-20、ADEKASTAB LA-7 7、ADEKASTAB LA-57 、 ADEKASTAB LA-67 、 ADEKASTAB LA-68 、 ADEKASTAB L A · 8 7 (以上均爲A D E K A公司製造,商品名 ),IRGANOX (註冊商標)1010、IRGANOX 1 03 5 ' IRGANOX 1 076、IRGANOX 1135、TINUVIN (註冊商標) 111FDL、TINUVIN 123、TINUVIN 144、TINUVIN 152、 TINUVIN 292、TINUVIN 5100(以上均爲日本汽巴公司製 造,商品名)等。 作爲過氧化物分解劑發揮作用之抗氧化劑,具體之化 合物列舉爲三苯基酸酯等磷系化合物、季戊四醇四月桂基 硫基丙酸酯、二月桂基硫基二丙酸酯、二硬脂基3,3’-硫二 丙酸酯等硫系化合物等。 過氧化物分解劑可爲市售者,列舉爲例如 ADEKASTAB TPP ( ADEKA 公司製造,商品名)、MARK AO-412S ( Adeka Argus化學公司製造,商品名)、 SUMILIZER (註冊商標)TPS (住友化學公司製造,商品 名)等。 -40- 201207555 上述抗氧化劑可單獨使用一種,亦可組合兩種以上使 用。 又一般而言,高分子材料由於吸收光,藉此引起分解 •劣化,故本發明之光硬化性熱硬化性樹脂組成物爲了進 行對紫外線之安定化對策,因而除上述抗氧化劑以外,亦 可使用紫外線吸收劑。 紫外線吸收劑列舉爲二苯甲酮衍生物、苯甲酸酯衍生 物、苯并***衍生物、三嗪衍生物、苯并噻唑衍生物、桂 皮酸酯(cinnamate )衍生物、鄰胺基苯甲酸酯衍生物、二 苯甲醯基甲烷衍生物等。二苯甲酮衍生物之具體例列舉爲 2-羥基-4-甲氧基二苯甲酮、2-羥基-4-正辛氧基二苯甲酮 、2,2’-二羥基-4-甲氧基二苯甲酮及2,4-二羥基二苯甲酮等 。苯甲酸酯衍生物之具體例列舉爲2-乙基己基水楊酸酯、 苯基水楊酸酯、對-第三丁基苯基水楊酸酯、2,4-二第三丁 基苯基-3,5-二第三丁基-4-羥基苯甲酸酯及十六烷基-3,5-二-第三丁基-4-羥基苯甲酸酯等。苯并***衍生物之具體 例列舉爲例如2- ( 2’-羥基-5’-第三丁基苯基)苯并***、 2- ( 2’-羥基- 5’-甲基苯基)苯并***、2- ( 2’-羥基- 3’-第 三丁基- 5’-甲基苯基)-5-氯苯并***、2- (2,-羥基-3,,5’-二-第三丁基苯基)-5-氯苯并***、2- (2,-羥基- 5’-甲基 苯基)苯并***及2- (2,-羥基-3,,5’-二-第三丁基苯基) 苯并***等。三嗪衍生物之具體例列舉爲羥基苯基三嗪、 雙乙基己氧基苯基甲氧基苯基三嗪等。Dyers and Colourists) issued) number. Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258 '266, 267, 268, 269. Diazo system: Pigment red 37, 38, 41. Soluble monoazo dye series: Pigment Red 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 52:2, 53:1, 53 :2, 57:1, 58:4, 63:1 ' 63:2, 64:1, 68. Benzimidazolone type: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208. Lanthanide: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224. Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 25 5, Pigment Red 2 64, Pigment Red 270, Pigment Red 272. Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 2 1 4, Pigment Red 2 2 0, Pigment Red 2 2 1 , Pigment Red 2 4 2 . Lanthanum: Pigment Red 168, Pigment Red 177, Pigment Red 216, Pigment -33- 201207555 Red 1 4 9 , Pigment Red 1 50, Solvent Red 5 2, Solvent Red 2 0 7. Quinacridone type: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209. Blue coloring agent: The blue coloring agent is a phthalocyanine system or an anthraquinone system, and the pigment system is classified into a pigment (Pigment). Specifically, it can be exemplified as follows: Pigment Blue 15, Pigment Blue 15:1 , Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60. For the dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue can be used. 70 and so on. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used. Green colorants: Green colorants also have phthalocyanine, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a ruthenium compound which is substituted with or without a metal may also be used. Yellow coloring agent: The yellow coloring agent is a monoazo-type diazo-based, a condensed azo-based, a benzimidazolone-based, an isoindolinone-based, an anthraquinone-based or the like, and specifically, the following are listed. -34- 201207555 惠醒系: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 1〇8, Pigment Yellow M3, Pigment Yellow 147, Pigment Yellow 199, _Huang 2〇^ / Isodecanone·Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185. Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180. Benzimidazolone: Pigment Yellow 12〇, Pigment Yellow 151, Pigment Yellow I54, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181. Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 1 (), 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 1〇4 , 105, 111, 116, 167, 168, 169, 182, 183. - azo system: pigment yellow 12, 13, 14, 16, 17, 55, 63, 81 '83, 87, 126, 127, 152' 170, 172, 174, 176, 188, 198 ° In addition, in order to adjust the color tone Colorants such as purple, orange, brown, and black can also be added. Specific examples are pigment purple 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, CI pigment orange 1, CI pigment orange 5, CI pigment orange 13, CI pigment orange 14, CI · pigment orange 16' CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51. C_I. Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like. -35-201207555 The blending ratio of the coloring agent is not particularly limited, but is preferably from 0 to 10 parts by mass, and most preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin. The compound having two or more ethylenically unsaturated groups in the photocurable thermosetting resin composition of the present invention is photohardened by irradiation of an energy ray to cause the carboxyl group-containing resin to be in an aqueous solution. Insoluble, or help insoluble. These compounds are conventionally used in the conventional polyester (meth) acrylate, polyether (methyl) propyl ester, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (A Base) acrylate and the like. Specifically, it is exemplified by alkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl methacrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates: N,N-dimethyl decylamine, N-hydroxymethyl decylamine, N,N-dimethylaminopropyl acrylamide, etc. Acrylamide N,N-dimethylamino Aminoalkyl acrylates such as ethyl acrylate and N,N-dimethylaminopropyl acrylate: hexanediol, trimethylolpropane, tetraol, dipentaerythritol, tris-hydroxyethyl isocyanuric acid a polyvalent acrylate such as an ester of ethylene oxide such as an acid ester, a propylene oxide adduct or an ε-hexane adduct; a phenoxy acrylate, a bisphenol sebacate, and Ethylene oxide adducts of such phenols or polyvalent acrylates such as propylene oxide; glycerol diglycidyl ether, glycerol trigest ether, trimethylolpropane triglycidyl ether, triglycidyl a polyvalent acrylate of a glycidyl ether such as a cyanoester; not limited to the above, but a polyether polyol, a polycarbonate diol, and a hydroxyl group It is preferred that the molecularly active basicity be a propyl acrylate such as acrylic acid propylene glycol; propylene pentaerythritol or lactone propylene glycerol uric acid may be a poly acrylate direct acrylate such as diene-36-201207555 or polyester polyol. Or acrylates and trimerates which are esterified with urethane by acid esters, and/or various methyl acrylates corresponding to the above acrylates. Further, an epoxy acrylate resin obtained by reacting a cresol novolak resin type epoxy resin epoxy resin with acrylic acid to exemplify a hydroxyl group of an epoxy acrylate resin and a hydroxy acrylate such as pentaerythritol tripropylene An epoxy group amino acid formate compound obtained by reacting a diisomeric carbamate compound such as isophorone diisocyanate. These epoxy propyl ester-based resins can improve photocurability without lowering the drying property. The compounding amount of the two or more ethylenically unsaturated groups in the molecule is from 5 to 100 parts by mass, more preferably from 1 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount is less than 5 parts by mass, the photocurability is lowered, and the active energy ray is difficult to form a pattern by alkali development, which is not preferable. On the other hand, when the amount is more than 1 part by mass, the solubility in the alkaline aqueous solution tends to become brittle, which is not preferable. The photocurable thermosetting resin composition of the present invention is a physical strength of the film, and may be formulated as needed. These may be filled with conventional inorganic or organic chelating agents, but particularly preferably used, spherical cerium oxide and talc. Further, metal hydroxides such as oxidized oxides and aluminum hydroxide may be used. Body pigments for white appearance or flame retardancy. The dosage of the stimulating agent is di-isocyanurate acrylate or the like, and the olefinic acid ester cyanate ester propylene finger-contact dry compound is preferably prepared at a blending rate, and when it is super, the coating film is high. The coating agent may be a barium sulphate titanium or a ruthenium sulphate, and 100 parts by mass of the resin containing a residue, preferably from 200 to 15 parts by mass, more preferably from 0.1 to 150 parts by mass, most preferably from -37 to 201207555. 1 to 1 part by mass. When the blending ratio of the ruthenium filler is more than 200 parts by mass, the viscosity of the composition becomes high, the printability is lowered, and the cured product becomes brittle, which is not preferable. Further, the photocurable thermosetting resin composition of the present invention may also use a binder polymer to improve dryness, dryness, and the like. For example, a polyester polymer 'polyurethane type polymer, a polyester urethane type polymer, a polyurethane polymer, a polyester urethane type polymer, a poly A amide-based polymer, a polyester amide-based polymer, an acrylic polymer, a cellulose-based polymer, a polylactic acid-based polymer, or a phenoxy-based polymer. These binder polymers may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be an elastomer or other elastomer containing a hydroxyl group to impart flexibility, to improve the brittleness of the cured product, and the like. For example, a polyester-based elastomer, a polyurethane-based elastomer, a polyester urethane-based elastomer, a polyamide-based elastomer, a polyester amide-based elastomer, an acrylic elastomer, or the like can be used. Olefin-based elastomer. Further, a resin obtained by modifying some or all of the epoxy groups having one or more kinds of epoxy resins to be a two-terminal carboxylic acid-modified butadiene-acrylonitrile rubber may be used. Further, a polybutadiene-based elastomer containing an epoxy group, a polybutadiene-based elastomer containing acrylic acid, or the like can be used. These elastomers may be used singly or in combination of two or more. Further, the photocurable thermosetting resin composition of the present invention may be used for the above-mentioned resin synthesis or composition of a carboxyl group-containing compound-38-201207555, or for coating on a substrate or a carrier film. Viscosity. Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; a cellosolve, a methyl cellosolve, or a butyl cellosolve; Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc.; ethanol, propanol Alcohols such as ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum brain, hydrogenated petroleum brain, and solvent petroleum brain. These organic solvents may be used singly or in combination of two or more. In general, when most of the polymer material starts to oxidize, subsequent oxidative degradation of the chain is caused, and the function of the polymer material is lowered, so that the photocurable thermosetting resin composition of the present invention can be added for use. (1) a radical scavenger that invalidates the generated radicals and/or (2) a peroxide decomposing agent that decomposes the generated peroxide into a harmless substance without generating new radicals. Oxidizer. Specific examples of the antioxidant which acts as a radical scavenger are hydroquinone, 4-tert-butylcatechol, 2-tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di -T-butyl-p-cresol, 2,2-methyl-bis(4-methyl-6-tert-butylphenol), 1,1,3-gin (2-methyl-4-) Hydroxy-5-third-39-201207555 butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (3,5-di-t-butyl-4-hydroxyl) Benzyl)benzene, 1,3,5-gin (3',5'-di-t-butyl-4-hydroxybenzyl)-3-trisole-2,4,6-(11^,311,51 A quinone compound such as quinone or a phenolic compound such as pyrogallol or benzoquinone, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or phenothiazine (Phenothiazin) An amine-based compound, etc. The radical scavenger can be commercially available, and is exemplified by, for example, ADEKASTAB (registered trademark) AO-30, ADEKASTAB AO-3 3 0 , ADEKASTAB AO-20, ADEKASTAB LA-7 7, and ADEKASTAB LA-57. , ADEKASTAB LA-67, ADEKASTAB LA-68, ADEKASTAB LA · 8 7 (all manufactured by ADEKA, trade name), IRGANOX (registered trademark) 1010, IRGANOX 1 03 5 'IRGANOX 1 076 , IRGANOX 1135, TINUVIN (registered trademark) 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (all of which are manufactured by Ciba Corporation, trade name), etc. As the oxidizing agent, specific compounds are exemplified by phosphorus compounds such as triphenyl ester, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-thiodipropionic acid. A sulfur-based compound such as an ester, etc. The peroxide-decomposing agent is commercially available, and is exemplified by, for example, ADEKASTAB TPP (manufactured by ADEKA Corporation, trade name), MARK AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), and SUMILIZER (registered). Trademark) TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc. -40- 201207555 The above antioxidants may be used singly or in combination of two or more. In general, polymer materials absorb light and cause decomposition. • Deterioration, the photocurable thermosetting resin composition of the present invention is prepared in addition to the above antioxidants in order to stabilize the ultraviolet rays. A UV absorber can be used. The ultraviolet absorber is exemplified by a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamate derivative, an ortho-aminobenzene. a formate derivative, a benzhydrylmethane derivative or the like. Specific examples of the benzophenone derivative are exemplified by 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, and 2,2'-dihydroxy-4- Methoxybenzophenone and 2,4-dihydroxybenzophenone. Specific examples of the benzoate derivative are exemplified by 2-ethylhexyl salicylate, phenyl salicylate, p-t-butylphenyl salicylate, and 2,4-di-t-butyl group. Phenyl-3,5-di-t-butyl-4-hydroxybenzoate and cetyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative are exemplified by, for example, 2-( 2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2'-hydroxy-5'-methylphenyl group. Benzotriazole, 2-( 2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-3,, 5'-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2,-hydroxy-5'-methylphenyl)benzotriazole and 2-(2,-hydroxy- 3,5'-di-t-butylphenyl) benzotriazole and the like. Specific examples of the triazine derivative are hydroxyphenyltriazine, bisethylhexyloxyphenylmethoxyphenyltriazine and the like.
紫外線吸收劑可爲市售者,列舉爲例如TINUVIN PS -41 - 201207555 、TINUVIN 99-2、TINUVIN 109、TINUVIN 384-2、 TINUVIN 900、TINUVIN 928、TINUVIN 1130、TINUVIN 400、TINUVIN 405、TINUVIN 460、TINUVIN 479 (以上 均爲日本汽巴公司製造,商品名)等。 上述之紫外線吸收劑可單獨使用一種,亦可組合兩種 以上使用,藉由與前述抗氧化劑倂用,可實現由本發明之 光硬化性熱硬化性樹脂組成物獲得之成形物之安定化》 本發明之光硬化性熱硬化性樹脂組成物可使用習知慣 用之N-苯基甘胺酸類、苯氧基乙酸類、噻吩氧基乙酸類、 毓基噻唑類等作爲鏈轉移劑以提高感度。列舉鏈轉移劑之 具體例時,爲例如毓基琥珀酸、锍基乙酸、毓基丙酸、蛋 胺酸、半胱胺酸、硫代水楊酸及其衍生物等具有羧基之鏈 轉移劑;毓基乙醇、疏基丙醇、锍基丁醇、锍基丙二醇、 毓基丁二醇、羥基苯硫醇及其衍生物等含有羥基之鏈轉移 劑;1-丁硫醇、丁基-3-毓基丙酸酯、甲基-3-巯基丙酸酯 、2,2-(伸乙二氧基)二乙烷硫醇、乙硫醇、4-甲基苯硫 醇、十二烷硫醇、丙硫醇、丁硫醇、戊硫醇、1-辛硫醇、 環戊硫醇、環己烷醇、硫代丙三醇、4,4-硫基雙苯硫醇等 〇 另外,可使用多官能性硫醇系化合物,且並無特別限 制,但可使用例如己烷-1,6-二硫醇、癸烷-1,10-二·硫醇、 二巯基二乙基醚、二锍基二乙基硫醚等脂肪族硫醇類,二 甲苯二硫醇、4,4’-二锍基二苯基硫醚、1,4-苯二硫醇等芳 香族硫醇類;乙二醇雙(锍基乙酸酯)、聚乙二醇雙(毓 -42- 201207555 基酸酯)、丙二醇雙(巯基乙酸酯)、甘油參(巯基乙酸 酯)、三羥甲基乙烷參(毓基乙酸酯)、三羥甲基丙烷參 (毓基乙酸酯)、季戊四醇肆(锍基乙酸酯)、二季戊四 醇陸(锍基乙酸酯)等多價醇之聚(锍基乙酸酯)類;乙 二醇雙(3-锍基丙酸酯)、聚乙二醇雙(3-毓基丙酸酯) 、丙二醇雙(3-锍基丙酸酯)、甘油參(3-巯基丙酸酯) 、三羥甲基乙烷參(锍基丙酸酯)、三羥甲基丙烷參(3-毓基丙酸酯)、季戊四醇肆(3-锍基丙酸酯)、二季戊四 醇陸(3-锍基丙酸酯)等多價醇之聚(3-巯基丙酸酯)類 ;1,4-雙(3-锍基丁氧基)丁烷、1,3,5-參(3-毓基丁氧基 乙基)-1,3,5-三嗪- 2,4,6 ( 1H,3H,5H)-三酮、季戊四醇肆 (3-毓基丁酸酯)等之聚(毓基丁酸酯)類。 該等市售品可列舉爲例如BMPA、MPM、EHMP、 NOMP ' MBMP 、 STMP 、 TMMP ' PEMP 、 DPMP 、及 TEMPIC (以上均爲堺化學工業(股)製造)、KARENZ ( 註冊商標)MT-PE1、KARENZ MT-BD1、及 KARENZ NR1 (以上爲昭和電工(股)製造)等。 另外,作爲鏈轉移劑發揮作用之具有巯基之雜環化合 物列舉爲例如毓基-4-丁內酯(別名:2-锍基-4-丁內酯) 、2-魏基-4-甲基-4-丁內醋' 2 -疏基-4-乙基-4-丁內醋、2-锍基-4-丁 硫內酯(Butyrothiolactone) 、2-巯基-4-丁內醯 胺、N -甲氧基-2 -疏基- ·4-丁內醯胺、N -乙氧基_2_疏基-4-丁 內醯胺、Ν -甲基-2-巯基-4-丁內醯胺、Ν -乙基-2-巯基-4-丁 內醯胺、Ν-(2 -甲氧基)乙基-2-锍基-4-丁內醯胺、Ν·( -43- 201207555 2 -乙氧基)乙基-2 -疏基-4-丁內醯胺、2 -硫基-5-戊內酯、 2-锍基-5-戊內醯胺、N-甲基-2-毓基-5-戊內醯胺、N-乙基-2-毓基-5-戊內醯胺、N- (2-甲氧基)乙基-2-毓基-5-戊內 酿胺、N- (2 -乙氧基)乙基-2-疏基-5-戊內酿胺、2 -疏基 苯并噻唑、2-毓基-5-甲硫基-噻二唑、2-毓基-6-己內醯胺 、2,4,6-三锍基+三嗪(三協化成(股)製造:商品名 DISUNETE F) 、2 -二丁胺基-4,6 -二毓基-S -三嗪(三協化 成(股)製造:商品名DISUNETE DB)、及2-苯胺基-4,6-二巯基-s-三嗪(三協化成(股)製造:商品名DISUNETE AF)等。 尤其,不損及光硬化性熱硬化性樹脂組成物之顯像性 之鏈轉移劑之具有巯基之雜環化合物較好爲锍基苯并噻唑 、3-毓基-4-甲基-4H-1,2,4-***、5-甲基-1,3,4-唾二唑-2-硫醇、1-苯基-5-锍基-1H-四唑。該等鏈轉移劑可單獨使用 或倂用兩種以上。 本發明之光硬化性熱硬化性樹脂組成物可使用密著促 進劑以提高層間之密著性、或感光性樹脂層與基材之密著 性。列舉具體之例時,有例如苯并咪唑、苯并噁唑、苯并 噻唑、2-毓基苯并咪唑、2-锍基苯并噁唑、2-锍基苯并噻 唑(商品名:川口化學工業(股)製造之AXEL Μ )、3-嗎啉基甲基-1-苯基-***-2-硫酮、5-胺基-3-嗎啉基甲基-噻唑-2-硫酮、2-毓基-5-甲硫基-噻二唑、***、四唑、苯 并***、羧基苯并***、含有胺基之苯并***、矽烷偶合 劑等。 • 44 - 201207555 本發明之光硬化性熱硬化性樹脂組成物可進一步視需 要添加微粉二氧化矽、有機膨潤土、蒙脫土、鋁碳酸鎂( hydrotalcite)等搖變化劑。作爲搖變化劑之經時安定性較 好爲有機膨潤土、鋁碳酸鎂,尤其是鋁碳酸鎂具有優異之 電特性。另外,可調配熱聚合抑制劑,或矽酮系、氟系、 高分子系等消泡劑及/或平流劑、咪唑系、噻唑系、*** 系等矽烷偶合劑、防銹劑、以及雙酚系、三嗪硫醇系等銅 害防止劑等習知慣用之添加劑類。 前述熱聚合抑制劑可用於防止前述聚合性化合物之熱 聚合或經時聚合。熱聚合抑制劑列舉爲例如4-甲氧基酚、 氫醌、烷基或芳基取代之氫醌、第三丁基兒茶酚、聯苯三 酚、2-羥基二苯甲酮、4-甲氧基-2-羥基二苯甲酮、氯化亞 酮、吩噻嗪、四氯苯醌(Chloranil )、萘胺、p-萘酚、 2,6-二-第三丁基-4-甲酚、2,2’-伸甲基雙(4-甲基-6-第三 丁基苯酚)、吡啶、硝基苯、二硝基苯、苦味酸(Picric acid) 、4-甲苯胺、甲基藍、與銅之有機螯合劑反應物、 水楊酸甲酯、及吩噻嗪、亞硝基化合物、亞硝基化合物與 A1之螯合物等。 本發明之光硬化性熱硬化性樹脂組成物係以例如前述 有機溶劑調整至適合塗佈方法之黏度,於基材上,藉由浸 塗法、流塗法、輥塗法、桿塗法、網版印刷法、簾塗法等 方法塗佈後,於約60〜100 °C之溫度,使組成物中所含之有 機溶劑揮發乾燥(暫時性乾燥),藉此形成無指觸黏性之 塗膜。隨後,藉由接觸方式(或非接觸方式),通過形成 -45- 201207555 有圖型之光罩選擇性地藉活性能量線加以曝光或利用雷射 直接曝光機等使圖型直接曝光,未曝光部以鹼性水溶液( 例如0.3〜3 %碳酸鈉水溶液)顯像而形成光阻圖型。進而, 於含有熱硬化性成分之組成物之情況,於例如約130-180 °C之溫度加熱而熱硬化,藉此使前述之含羧基之樹脂之羧 基與分子中具有2個以上環狀醚基及/或環狀硫醚基之熱硬 化性成分反應,可形成耐熱性、耐藥品性、耐吸濕性、密 著性、電特性等諸特性均優異之硬化塗膜。又,爲了即使 未含熱硬化性成分時,藉由熱處理,亦可使在曝光時未反 應之狀態之剩餘殘留光硬化性成分之乙烯性不飽和鍵進行 熱自由基聚合,而提高塗膜特性,故亦可依據目的•用途 ,經熱處理(熱硬化)。 至於上述基材,除了預先形成電路之印刷配線板或可 撓性印刷配線板以外,可使用紙-酚樹脂、紙-環氧樹脂、 玻璃布-環氧樹脂 '玻璃-聚醯亞胺、玻璃布/不織布-環氧 樹脂、玻璃布/紙-環氧樹脂、合成纖維-環氧樹脂、氟樹脂 •聚乙烯· PPO ·氰酸酯等之複合材之所有等級(FR-4等 )之貼銅層合板、聚醯亞胺薄膜、PET薄膜、玻璃基板、 陶瓷基板、晶圓板等。 本發明之光硬化性熱硬化性樹脂組成物塗佈後進行之 揮發乾燥,可使用熱風循環式乾燥爐、IR爐、加熱板、通 氣烘箱等(使用具備由蒸氣引起之空氣加熱方式之熱源者 之乾燥機內之熱風對流接觸之方法以及由噴嘴吹拂支持體 之方式)進行。 -46- 201207555 如下塗布本發明之光硬化性熱硬化性樹脂組成物,經 揮發乾燥後,對所得塗膜進行曝光(活性能量線之照射) 。塗膜於曝光部(以活性能量線照射之部分)經硬化。 作爲用於上述活性能量線照射之曝光機,可使用直接 描繪裝置(例如由自電腦之CAD數據以直接雷射描繪圖像 之雷射直接呈像裝置),搭載金屬鹵素燈之曝光機、搭載 (超)高壓水銀瞪之曝光機、搭載水銀短弧氙燈之曝光機 ,或者使用(超)高壓水銀燈等紫外線燈之直接描繪裝置 。至於活性能量線,只要使用最大波長在350〜410nm範圍 之雷射光,則爲氣體雷射、固體雷射任一者均可。又,其 曝光量隨著膜厚等而異,但一般可爲5〜500 mJ/cm2,較好 爲10〜3 00 mJ/cm2之範圍。作爲上述直接描繪裝置,可使 用例如日本ORBETECH公司製、PENTAX公司製等者,只 要爲使最大波長爲3 5 0〜41 Onm之雷射光震盪之裝置即可而 可使用任何裝置。 至於前述顯像方法,可以浸漬法、淋洗法、噴霧法、 刷塗法等,使用氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、 磷酸鈉、矽酸鈉、氨、胺類等之鹼水溶液作爲顯像液而進 行。 本發明之光硬化性熱硬化性樹脂組成物,除以液狀直 接塗佈於基材上之方法以外,亦可以將阻焊劑預先塗佈於 聚對苯二甲酸乙二酯等薄膜上並經乾燥,形成具有阻焊劑 層之乾膜之形態使用。使用本發明之光硬化性熱硬化性樹 脂組成物作爲乾膜之情況示於下。 -47- 201207555 乾膜爲具有以載體薄膜、阻焊劑層、及視需要使用之 可剝離之覆蓋層之順序層合而成之構造者。阻焊劑層爲將 鹼顯像性之光硬化性熱硬化性樹脂組成物塗佈於載體薄膜 或覆蓋薄膜上並經乾燥獲得之層,於載體薄膜上形成阻焊 劑層後,將覆蓋薄膜層合於其上,於覆蓋膜上形成阻焊劑 層,且將該層合物層合於載體薄膜上即可獲得乾膜。 至於載體薄膜係使用厚度2〜150 μιη之聚酯薄膜等熱可 塑性薄膜。 阻焊劑層系將鹼顯像性光硬化性熱硬化性樹脂組成物 以刮板塗佈器、模唇塗佈器、科馬塗佈器、薄膜塗佈器等 ,以10〜150μιη之厚度均勻的塗佈於載體薄膜或覆蓋薄膜上 並經乾燥而形成。 但 膜疊層加一 , 護重劑、任 等 保材焊像之 膜 久基阻顯後 薄 永之成、光 烯 。{路形光曝 丙者膜電上曝或 聚心護成材行前 、Μ/保形基進光 膜薄作與之樣曝 薄IIV製層路同在 嫌載上劑電述體 乙比板焊成前載 聚力線阻形與 。 用著配將於,膜 使接刷,,層塗 可之印離合劑化 膜層之剝貼焊硬 。 薄劑膜膜等阻成可 蓋焊乾薄機之形即 覆阻用蓋合成可離 於與使覆層形,剝 至爲於將用於化下 好 係使對硬況 較 },。熱情 [實施例] 以下例示實施例及比較例具體說明本發明,但本發明 並不受下述實施例之限制。又,以下之「份」及「%」若 -48- 201207555 無特別說明則全部爲質量基準。 合成例1 於具備溫度計、氮氣導入裝置以及環氧烷導入裝置及 攪拌裝置之高壓釜中’饋入酚醛清漆型甲酚樹脂(昭和高 分子(股)製造,商品名「SHONOL CRG951」,OH當量 :1 1 9 _ 4 ) 1 1 9 · 4份、氫氧化鉀1 · 1 9份及甲苯1 1 9 · 4份,經攪 拌且使該系統經氮氣置換,並經加熱升溫。接著,緩慢滴 加環氧丙院63·8份,在125~132°C、0〜4.8 kg/cm2反應16小 時。隨後,冷卻至室溫,於該反應溶液中添加混合8 9 %磷 酸1.56份,中和氫氧化鉀,獲得不揮發份62.1%、羥基價 182.2 g/eq之酚醛清漆型甲酚樹脂之環氧丙烷反應溶液。 其係酚性羥基每1當量平均加成1.08莫耳之烷氧烷者。 接著,將所得酚醛清漆型甲酚樹脂之環氧烷反應溶液 293.0份、丙烯酸43.2份、甲烷磺酸11.53份、甲基氫醌 0.1 8份及甲苯252.9份饋入具備攪拌機、溫度計及空氣吹入 管之反應器中,以10ml/分鐘之速度吹入空氣,邊攪拌邊 在1 1 〇 °C反應1 2小時。因反應產生之水以與甲苯之共沸混 合物餾出1 2.6份之水。隨後,冷卻至室溫,所得反應溶液 以1 5 %氫氧化鈉水溶液3 5.3 5份中和,接著以水洗淨。隨後 ,以蒸發器邊以二乙二醇單乙基醚乙酸酯118」份置換甲 苯邊餾除,獲得酚醛清漆型丙烯酸酯樹脂溶液。接著’將 所得酚醛清漆型丙烯酸酯樹脂溶液332·5份及三苯基膦i·22 份饋入具備攪拌器、溫度計及空氣吹入管之反應器中,以 -49- 201207555 10ml/分鐘之速度吹入空氣,邊攪拌邊緩緩添加四氫苯二 甲酸酐60.8份,在95~101°C反應6小時。獲得固體成分之 酸價8811^1<:011/8,不揮發份71%之含有羧基之感光性樹脂 之樹脂溶液。以下,將其稱爲漆料A-1。 合成例2 於具備溫度計、攪拌機及回流冷凝器之5升可分離燒 瓶中饋入作爲聚合物多元醇之聚己內酯二醇(Daicel化學 工業(股)製造之PLACCEL208,分子量830 ) 1,245份、 作爲具有羧基之二羥基化合物之二羥甲基丙酸201份、作 爲聚異氰酸酯之異佛爾酮二異氰酸酯777份及作爲具有羥 基之(甲基)丙烯酸酯之丙烯酸2 -羥基乙酯119份,接著 分別注入0.5份之對-甲氧基苯酚及二-第三丁基羥基甲苯。 邊攪拌邊加熱至60 °C後停止加熱,添加二月桂酸二丁基錫 0.8份。於反應容器內之溫度開始下降時再度加熱,且在 80°C持續攪拌,以紅外線吸收光譜確認異氰酸酯基之吸收 光譜(2280CHT1 )消失時結束反應,獲得黏稠液體之胺基 甲酸酯丙烯酸酯化合物。使用卡必醇乙酸酯調整至不揮發 份=50質量%。獲得固體成分之酸價47 mgKOH/g,不揮發 份5 0%之具有羧基之胺基甲酸酯(甲基)丙烯酸酯化合物 之樹脂溶液。以下,將其稱爲漆料A-2。 合成例3 於具備攪拌機、溫度計、回流冷凝器、滴加漏斗及氮 -50- 201207555 氣導入管之二升可分離燒瓶中添加作爲溶劑之二乙二醇二 甲基醚900份,及作爲聚合起始劑之第三丁基過氧基2-乙 基己酸酯(日本油脂(股)製造,商品名:PERBUTYL Ο )21.4份’加熱至90°C。加熱後,將甲基丙烯酸309.9份、 甲基丙烯酸甲酯116.4份、及內酯改質之甲基丙烯酸2-羥基 乙酯(PLACCELFMl:Daicel化學工業(股)製造) 109.8份與聚合起始劑之雙(4-第三丁基環己基)過氧基二 碳酸酯(日本油脂(股)製造,商品名;PEROYL TCP ) 21.4份於3小時內一起滴加於其中,接著熟成6小時,藉此 獲得含有羧基之共聚合樹脂。又,反應係在氮氣氛圍下進 行。 接著,將甲基丙烯酸3,4-環氧基環己酯(Daicel化學 工業(股)製造,商品名;CYCLOMER A200 ) 363.9份、 作爲開環觸媒之二甲基苄基胺3 ·6份、作爲聚合抑制劑之 氫醌單甲基醚1.80份加入含有羧基之其聚合樹脂,加熱至 1 00 °C,藉由攪拌進行環氧基之開環加成反應。16小時後 ,獲得固體成分酸價爲108.9 mgKOH/g、重量平均分子量 25,000,固體成分54%之樹脂溶液。以下將其稱爲漆料A-3 合成例4 於二乙二醇單乙基醚乙酸酯650份中饋入鄰甲酚酚醛 清清型環氧樹脂(DIC (股)製造’ EPICLON N-695 ’軟 化點95。(:,環氧當量214,平均官能基數7.6) 1070份(縮 201207555 水甘油基數(芳香環總數):5.0莫耳)、丙烯酸360份( 5.〇莫耳)、及氫醌1.5份,加熱攪拌至l〇〇°C ’均勻溶解。 接著,饋入三苯基膦4 · 3份’加熱至1 1 〇 °C且反應2小時後 ,再追加三苯基膦1.6份,升溫至1 2 0 °C再進行反應1 2小時 。於所得反應液中饋入芳香族烴(SOLVESSO 1 50 ) 525份 、四氫苯二甲酸酐608份(4.0莫耳),在110 °C進行反應4 小時。接著,於所得反應液中饋入甲基丙烯酸縮水甘油酯 142.0份(1.0莫耳),在115°C進行反應4小時,獲得固體 成分酸價77 mgKOH/g,固體成分65%之樹脂溶液。以下將 其稱爲漆料R-1。 合成例5 於二乙二醇單乙基醚乙酸酯6 00份中饋入鄰甲酚酚醛 清清型環氧樹脂(DIC (股)製造,EPICLON N-695,軟 化點95 °C,環氧當量214,平均官能基數7.6) 1 070份(縮 水甘油基數(芳香環總數):5.0莫耳)、丙烯酸360份( 5.0莫耳)、及氫醌1.5份,加熱攪拌至100°C,均勻溶解。 接著,饋入三苯基膦4.3份,加熱至1 10t且反應2小時後 ,升溫至120°C再進行反應12小時’。於所得反應液中饋入 芳香族烴(SOLVESSO 150) 415份、四氫苯二甲酸酐 45 6.0份(3.0莫耳),在1 l〇°C進行反應4小時。經冷卻後 ,獲得固體成分酸價89 mgKOH/g,固體成分65%之樹脂溶 液。以下將其稱爲漆料R-2。 •52- 201207555 合成例6 饋入甲酚酚醛清漆型環氧樹脂(日本化藥(股)製造 ,EOCN-104S,軟化點 92°C,環氧當量 220) 2200份、二 羥甲基丙酸134份、丙烯酸648.5份、甲基氫醌4.6份、卡必 醇乙酸酯1131份及溶劑油(Solvent naphtha) 484.9份,加 熱至9.0°C並攪拌,使反應混合物溶解。接著,使反應液 冷卻至60°C,饋入三苯基膦13.8份,加熱至100°C,反應 約32小時,獲得酸價爲0.5 mgKOH/g之反應物。接著,於 其中饋入四氫苯二甲酸酐364.7份、卡必醇乙酸酯137.5份 及溶劑油58.8份,加熱至95 °C,反應約6小時,經冷卻, 獲得固體成分酸價40 mgKOH/g,不揮發份65%之含有羧基 之感光性樹脂之樹脂溶液。以下將其稱爲漆料R-3。 合成例7 使環氧當量800、軟化點79 °C之雙酚F型固型環氧樹脂 400份溶解於表氯醇925份與二甲基亞碾462.5份後,於攪 拌下在70°C於100分鐘內添加98.5%之NaOH 8 1.2份。添加 後再於70 °C進行反應3小時。接著,減壓餾除過量之未反 應表氯醇及二甲基亞颯之大半,將含有副生鹽及二甲基亞 碾之反應產物溶解於甲基異丁基酮750份中,接著添加 3 0%NaOH 10份,在70°C反應1小時。反應結束後,以200 份水進行水洗兩次。油水分離後’自油層蒸餾回收甲基異 丁基酮,獲得環氧當量290、軟化點62 °C之環氧樹脂(a-1 )3 7 0份。饋入所得環氧樹脂(a- 1 ) 2900份(10當量)、 -53- 201207555 丙烯酸720份(l〇當量)、甲基氫醌2.8份、卡必醇乙酸酯 1 9 5 0份,加熱至9 0 °C ’經攪拌’使反應混合物溶解。接著 ,使反應液冷卻至60 °C ’饋入三苯基膦16.7份,加熱至 1〇〇。(:,反應約3 2小時,獲得酸價1.〇11^1(:01^8之反應物》 接著,於其中饋入琥珀酸酐786份(7·86莫耳)、卡必醇 乙酸酯423份,加熱至95°C,進行反應約6小時,獲得固體 成分酸價1〇〇 mgKOH/g、固體成分65%之樹脂溶液。以下 將其稱爲漆料R-4。 實施例1〜13及比較例1~3 使用上述合成例之樹脂溶液,與下述表1所示之各種 成分一起調配成表1所示之比例(質量份),以攪拌機預 混合後,以三根輥硏磨機混練,調製阻焊劑用感光性樹脂 組成物。此處,以ERIKSEN公司製造之粒度測定器進行粒 度測定該所得感光性樹脂組成物之分散度並經評價,爲 1 5 μιη以下。 -54- 201207555 【表1】 組成 (質量份) . 度施例 ±m 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 A-1 141 141 141 141 141 141 141 \Ai δδ 的 dd 71 141 141 A-2 6ΰ A-3 $6 漆料 R-1 11 R-2 1b4 r-3 46 r-4 154 也取么 (Β-1Γ1 IS 舰劑 1 (B-3)·4 1.5 1.5 1.5 1.5 1.5 i.i 1.5 1.S 1.S 1.5 1.5 1.6 \.b 1.5 1.5 HP-4032*4 20 20 20 20 10 10 id iO 2ΰ ίύ Ο) 20 2Q VI^4700CA90,,:, 2ί 13 iSN355CA9(T。 zi 13 T04PCA75,, ib —著龟劑*β 0.3 0.3 ΰ.3 ΰ.3 0.3 0.3 0.3 0.3 ύ.3 0.5 0.3 0.3 0.3 o.a ΰΛ 0.3 u 0.8 ύ.6 0.6 0.8 O.d 0·δ ΰ.ό 0.8 ύ.6 0.6 0.8 ύ.8 0.6 ύ.ύ ύ.ύ U.tt 吩噻嗪 O.t 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 AXELMPIU 0.2 0.2 ύ.2 ό.2 ο.ί 0.5 Ο.ί 0.2 0.2 6.2 ύΛ 0.2 0.2 0.2 ύΛ IRGANOXIOtO*" 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 B-33 *12 260 2όύ 200 ίύό 2。0 200 ίύύ 佥όο 2όύ 200 206 ίύό ίόό ίύο 200 ACTINYLAM*,J 25ΰ DHT-4A*m 5 5 S 5 5 5 S 5 S 5 S S 5 S b 5 消泡劑 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 A-dcp* ,a 5 5 5 S S 5 S 5 δ 5 ί 5 5 5 S 5 DPHA • _ o 1S IS 15 a 15 15 1古 IS 15 15 15 15 15 15 u> ii 1 PA-B80E*" 17.5 Mw-100LM"ie 12.5 ♦1 : 2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮(IRGACURE 907:日本汽巴公司製) *2 : 2,4*二乙基噻噸酮(1〇1^人01;11£0孤-3:曰本化薬挪:〉公司製) *3 :乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-昨哩-3-基]-1,1-(0-乙醯蹄 (IRGACURE OXE 02:日本汽巴公司製) *4 :萘環氧樹脂(DIC(股)製) »5 :萘環麵脂(DIC(股)製)HP-4700之卡必醇乙酸酯截取品個體成分90%) »6 :萘環氧樹脂(東都化成(股)製)ESN355之卡必醇乙酸酯截取品個體成分90%) *7 :甲酚酚醛清漆環氧樹脂凍都化成(股)製)704P之卡必酵乙酸醋截取品(固體成分75%) *8 : C.I.顔料藍 15:3 *9 : C.I.顏料黃 147 *10 ·· 2-疏基苯并噻唑 備*11 :抗氧化劑(日本汽巴公司製) 註*12 :硫酸鋇(堺化學工業(股)製) *13 :由球狀二氧化砂與板狀髙嶺土構成之化合物的SILLITIN之胺基矽烷偶合劑材料處理品(HOFFMANN MINERAL公司製) *14 ··水滑石(協和化學工業(股)製) *15 :二乙二薛單***乙酸醋 *16 :二季戊四醇六丙烯酸醋 *17 :獅異瓿酸酯(旭化成Chemicals(股)製) *18 :甲基化三聚氛胺樹脂(三和化學(股)製) 性能評價: <最適曝光量> 使銅厚18μπι之電路圖型基板經銅表面粗化處理(MEC (股)製造之MEC ETCH BOND CZ-8100)後,經水洗、 乾燥後,以網版印刷法全面地塗佈前述實施例及比較例之 -55- 201207555 光硬化性熱硬化性樹脂組成物,以80。(:之熱風循環式乾燥 爐乾燥60分鐘。乾燥後,使用搭載高壓水銀燈之曝光裝置 ’透過階變圖(Step Tablet) (Kodak No.2)曝光,進行 顯像(30°C,0.2MPa,lwt%碳酸鈉水溶液)60秒時殘留 之階變圖之圖型爲7段時作爲最適曝光量。 <顯像性> 利用網版印刷法,以使乾燥後之膜厚成爲約25 μπι之方 式’將前述實施例及比較例之光硬化性熱硬化性樹脂組成 物塗佈於銅裸基板上,以80°C之熱風式循環式乾燥爐乾燥 3 0分鐘。乾燥後,以lwt%之碳酸鈉水溶液進行顯像,利用 碼錶計測直到乾燥塗膜去除之時間。 <最大顯像壽命> 以網版印刷將前述實施例及比較例之組成物全面塗佈 於形成圖型之銅箔基板上,在80°C下乾燥20分鐘至80分鐘 ,且每10分鐘取出基板,放冷至室溫。以壓製壓力0.2MP a 之條件對該基板,以30°C之lwt%碳酸鈉水溶液進行顯像60 秒,以未殘留殘渣之最大容許乾燥時間作爲最大顯像壽命 <觸黏性> 以網版印刷將前述實施例及比較例之組成物全面塗佈 於形成圖型之銅箔基板上,以80°C之熱風循環式乾燥爐乾 -56- 201207555 燥30分鐘’放冷至室溫。使PET製之負型薄膜接觸該基板 ,以〇RC公司製造之HMW_GW2〇,於減壓條件下壓著1分 鐘’隨後’以下列基準評價剝離負型薄膜時之薄膜貼合狀 態。 〇:剝離薄膜時,完全無受阻,無塗膜殘留痕跡 △:剝離薄膜時,僅稍受阻,塗膜痕跡少 X ··剝離薄膜時,受阻且塗膜痕跡清楚 特性試驗: 以網版印刷將前述實施例及比較例之組成物全面塗佈 於形成圖型之銅箔基板上.,以80°c乾燥30分鐘,且放冷至 室溫。對該基板,使用搭載高壓水銀燈之曝光裝置,以最 適曝光量使阻焊劑圖型曝光,以3 0 °C之1 wt%碳酸鈉水溶液 ,以噴佈壓力〇.2MPa之條件進行顯像90秒,獲得光阻圖型 。利用UV輸送爐,以累積曝光量1000 mj/cm2之條件對該 基板照射紫外線後,在1 5 0 °C加熱60分鐘硬化。對所得印 刷基板(評價基板)評價如下特性。 <耐酸性> 在室溫下’將評價基板浸漬於10v〇l%H2SO4水溶液中 3 0分鐘,以目視確認滲入或塗膜之溶出,再利用膠帶剝離 確認剝離。 〇:確認沒有變化者 △:僅少許變化 -57- 201207555 X:塗膜膨脹造成膨潤脫落者 <耐鹼性> 在室溫下,將評價基板浸漬於10vol%NaOH水溶液中 3 0分鐘,以目視確認滲入或塗膜之溶出,再利用膠帶剝離 確認剝離。 〇:確認沒有變化者 △:僅少許變化 X:塗膜膨脹造成膨潤脫落者 <焊料耐熱性> 將塗佈有松脂系助熔劑之評價基板浸漬於預先設定在 260 °C之焊料槽中,以改質醇洗淨助熔劑後,以目視評價 光阻劑層之膨脹•剝離。判定基準如下。 〇:重複3次以上之浸漬1 0秒亦未見到剝離 △:重複3次之浸漬1 0秒後少許剝離 X : 3次以內之浸漬1 0秒後光阻層膨脹、剝離 <耐無電解鍍金性> 使用市售品之無電解鍍鎳浴及無電解鍍金浴,在鎳5 μηι、金〇 . 〇 5 μιη之條件下進行電鍍,以膠帶剝離評價阻劑層 是否有剝離,以及電鍍滲入之有無後,以膠帶剝離評價阻 劑層是否有剝離。判定基準如下。 〇:電鍍後確認僅有少許滲入’但膠帶剝離後無剝離 -58- 201207555 △:電鍍後確認僅少許滲入,且在膠帶剝離後亦發現 剝離 X :電鍍後產生剝離 < p c τ耐性> 使用PCT裝置(ESPEC (股)製造之HAST SYSTEM TPC- 412MD),在121°C、飽和、0.2MPa之條件下處理形 成阻焊劑硬化塗膜之評價基板168小時,評價塗膜之狀態 。判斷基準如下。 〇:無膨脹、剝離、變色、溶出者 △:僅少許膨脹、剝離、變色、溶出者 X:發現多處之膨脹、剝離、變色、溶出者 <冷熱衝擊耐性> 製作具有形成沖壓出□、〇圖型之阻焊劑硬化塗膜之 評價基板。所得評價基板以冷熱衝擊試驗器(ETAC (股 )製造),以-55°C/30分鐘〜150°C/30分鐘作爲一循環,進 行1 000次循環之耐性試驗。試驗後,以目視觀察處理後之 硬化膜,且以下列基準判斷龜裂之發生狀況。 〇:龜裂發生率未達30% △:龜裂發生率30〜50% X :龜裂發生率超過50% <HAST特性> -59- 201207555 於形成梳型電極(線/間隔=50微米/50微米)之BT基 板上形成阻焊劑硬化塗膜,作成評價基板。將該評價基板 放入130°C、濕度85%之氛圍下之高溫高濕槽中,以電壓 12V進行荷電,進行槽內HAST試驗168小時。依據下列判 斷基準評價經過1 68小時時之槽內絕緣電阻値。 〇:超過108Ω △ : 106~108Ω X :未達1〇6Ω 前述各評價試驗之結果示於下表2。 【表2】The ultraviolet absorbers are commercially available, and are listed, for example, as TINUVIN PS-41 - 201207555, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (all of which are manufactured by Japan Ciba, trade name). The above-mentioned ultraviolet absorbers may be used singly or in combination of two or more kinds, and the stability of the molded article obtained from the photocurable thermosetting resin composition of the present invention can be achieved by using the above-mentioned antioxidant. As the photocurable thermosetting resin composition of the invention, a conventionally used N-phenylglycine, phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole or the like can be used as a chain transfer agent to improve sensitivity. Specific examples of the chain transfer agent include a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof. a hydroxyl group-containing chain transfer agent such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and its derivatives; 1-butanethiol, butyl- 3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2-(ethylenedioxy)diethanethiol, ethyl mercaptan, 4-methylbenzenethiol, dodecane Mercaptan, propanethiol, butanol, pentyl mercaptan, 1-octyl mercaptan, cyclopentanethiol, cyclohexane alcohol, thioglycerol, 4,4-thiobisbenzenethiol, etc. A polyfunctional thiol compound can be used without particular limitation, but for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether can be used. An aliphatic thiol such as dimercaptodiethyl thioether, an aromatic thiol such as xylene dithiol, 4,4'-dimercaptodiphenyl sulfide or 1,4-benzenedithiol ; ethylene glycol bis(mercaptoacetate), polyethylene glycol double (毓-42- 201207555 amide), propylene glycol bis(mercaptoacetate), glycerol ginseng (mercaptoacetate), trimethylolethane thiol (mercaptoacetate), trimethylolpropane ginseng Poly(mercaptoacetate) of polyvalent alcohols such as pentaerythritol), pentaerythritol (mercaptoacetate), dipentaerythritol (mercaptoacetate); ethylene glycol bis(3-indenyl) Propionate), polyethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), glycerol (3-mercaptopropionate), trimethylolethane (mercaptopropionate), trimethylolpropane ginseng (3-mercaptopropionate), pentaerythritol bismuth (3-mercaptopropionate), dipentaerythritol (3-mercaptopropionate), etc. Poly(3-mercaptopropionate) of the valency alcohol; 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-gin(3-mercaptobutoxyethyl)- Poly(indenyl butyrate) such as 1,3,5-triazine-2,4,6 (1H,3H,5H)-trione or pentaerythritol bismuth (3-mercaptobutyrate). Such commercially available products can be exemplified by, for example, BMPA, MPM, EHMP, NOMP 'MBMP, STMP, TMMP 'PEMP, DPMP, and TEMPIC (all of which are manufactured by 堺Chemical Industries Co., Ltd.), KARENZ (registered trademark) MT-PE1 , KARENZ MT-BD1, and KARENZ NR1 (above are manufactured by Showa Denko). Further, the heterocyclic compound having a mercapto group functioning as a chain transfer agent is exemplified by, for example, mercapto-4-butyrolactone (alias: 2-mercapto-4-butyrolactone), 2-weiyl-4-methyl group -4-butyrol vinegar '2-sulfo-4-ethyl-4-butyrolactone, 2-mercapto-4-butane lactone (Butyrothiolactone), 2-mercapto-4-butylidene, N -Methoxy-2-carbyl--4-butyrolactam, N-ethoxy-2-sulfo-4-butylidene, Ν-methyl-2-mercapto-4-butene Amine, Ν-ethyl-2-mercapto-4-butylidene, Ν-(2-methoxy)ethyl-2-mercapto-4-butylidene, Ν·( -43- 201207555 2 -ethoxy)ethyl-2-carbo-4-butylidene, 2-thio-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2- Mercapto-5-valeroinamide, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2-indolyl-5-pentane , N-(2-ethoxy)ethyl-2-sulfo-5-pentalactam, 2-phenylbenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2- Mercapto-6-caprolactam, 2,4,6-tridecyl+triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name DISUNETE F), 2-dibutylamino-4,6-di ki-S-triazine Sankyo Chemical Co., Ltd. manufactures: trade name DISUNETE DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name DISUNETE AF). In particular, the heterocyclic compound having a mercapto group of a chain transfer agent which does not impair the developability of the photocurable thermosetting resin composition is preferably mercaptobenzothiazole or 3-mercapto-4-methyl-4H- 1,2,4-triazole, 5-methyl-1,3,4-septadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole. These chain transfer agents may be used singly or in combination of two or more. In the photocurable thermosetting resin composition of the present invention, an adhesion promoter can be used to improve the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Kawaguchi) AXEL(R) manufactured by Chemical Industry Co., Ltd., 3-morpholinylmethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-sulfur Ketone, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, benzotriazole containing an amine group, decane coupling agent and the like. • 44 - 201207555 The photocurable thermosetting resin composition of the present invention may further contain a powder shaker such as fine powder of ceria, organic bentonite, montmorillonite or hydrotalcite as needed. The stability over time as a shake change agent is preferably excellent for organic bentonite, aluminum magnesium carbonate, and especially aluminum magnesium carbonate. In addition, a thermal polymerization inhibitor, an antifoaming agent such as an anthrone, a fluorine or a polymer, and/or a leveling agent, a decane coupling agent such as an imidazole type, a thiazole type or a triazole type, a rust preventive agent, and a double can be used. A conventionally used additive such as a phenol-based or triazine thiol-based copper-preventing agent. The aforementioned thermal polymerization inhibitor can be used to prevent thermal polymerization or time-lapse polymerization of the aforementioned polymerizable compound. The thermal polymerization inhibitor is exemplified by, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, tert-butylcatechol, biphenyltriol, 2-hydroxybenzophenone, 4- Methoxy-2-hydroxybenzophenone, chlorinated ketone, phenothiazine, Chloranil, naphthylamine, p-naphthol, 2,6-di-t-butyl-4- Cresol, 2,2'-extended methyl bis(4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, Methyl blue, organic chelating agent reactant with copper, methyl salicylate, and phenothiazine, nitroso compound, chelating compound of nitroso compound and A1, and the like. The photocurable thermosetting resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, the organic solvent, and is applied to a substrate by a dip coating method, a flow coating method, a roll coating method, a rod coating method, or the like. After coating by a screen printing method or a curtain coating method, the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of about 60 to 100 ° C, thereby forming a finger-free tack. Coating film. Subsequently, by means of contact (or non-contact), by forming a -45-201207555 patterned mask, the active energy line is selectively exposed or directly exposed by a laser direct exposure machine, etc., without exposure The portion is developed with an alkaline aqueous solution (for example, 0.3 to 3% aqueous sodium carbonate solution) to form a photoresist pattern. Further, in the case of a composition containing a thermosetting component, it is heated and cured at a temperature of, for example, about 130 to 180 ° C, whereby the carboxyl group of the carboxyl group-containing resin and the molecule have two or more cyclic ethers. The thermosetting component of the group and/or the cyclic thioether group reacts to form a cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. In addition, in order to improve the coating film characteristics, the ethylenically unsaturated bond of the remaining residual photocurable component in the unreacted state at the time of exposure can be thermally radically polymerized by heat treatment even when the thermosetting component is not contained. Therefore, it can be heat treated (thermosetting) according to the purpose and use. As the above substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimine, glass can be used. Cloth/non-woven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin, polyethylene, PPO, cyanate ester, etc. All grades (FR-4, etc.) Copper laminate, polyimide film, PET film, glass substrate, ceramic substrate, wafer board, and the like. The photocurable thermosetting resin composition of the present invention is subjected to volatilization and drying after application, and a hot air circulation type drying furnace, an IR furnace, a heating plate, a ventilating oven, or the like (using a heat source having a heating method by air caused by steam) can be used. The hot air convection contact method in the dryer and the manner in which the support is blown by the nozzle are performed. -46-201207555 The photocurable thermosetting resin composition of the present invention is applied as follows, and after evaporation and drying, the obtained coating film is exposed (irradiation of active energy rays). The coating film is hardened at the exposed portion (the portion irradiated with the active energy ray). As an exposure machine for the above-described active energy ray irradiation, a direct drawing device (for example, a laser direct image forming device that directly draws an image from a CAD data of a computer) can be used, and an exposure machine equipped with a metal halide lamp can be mounted. (Ultra) high-pressure mercury enamel exposure machine, exposure machine equipped with mercury short-arc xenon lamp, or direct drawing device using ultraviolet light such as (ultra) high-pressure mercury lamp. As for the active energy ray, any one of a gas laser and a solid laser can be used as long as the laser light having a maximum wavelength of 350 to 410 nm is used. Further, the amount of exposure varies depending on the film thickness, etc., but it is usually in the range of 5 to 500 mJ/cm2, preferably 10 to 300 mJ/cm2. As the direct drawing device, for example, a device manufactured by ORBETECH Co., Ltd., PENTAX Corporation, or the like can be used, and any device can be used as long as the device can oscillate laser light having a maximum wavelength of 550 to 41 Onm. As for the above-mentioned developing method, a dipping method, a rinsing method, a spraying method, a brushing method, or the like may be used, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia, an amine or the like may be used. The aqueous alkali solution is carried out as a developing solution. The photocurable thermosetting resin composition of the present invention may be applied to a film such as polyethylene terephthalate or the like in advance, in addition to the method of directly applying the liquid to the substrate. It is dried and formed into a form of a dry film having a solder resist layer. The case where the photocurable thermosetting resin composition of the present invention is used as a dry film is shown below. -47- 201207555 The dry film is a structure having a carrier film, a solder resist layer, and a peelable cover layer as needed. The solder resist layer is a layer obtained by applying an alkali developable photocurable thermosetting resin composition onto a carrier film or a cover film and dried, and after forming a solder resist layer on the carrier film, the cover film is laminated. A solder resist layer is formed on the cover film, and the laminate is laminated on the carrier film to obtain a dry film. As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used. In the solder resist layer, the alkali-developing photocurable thermosetting resin composition is uniform in thickness of 10 to 150 μm by a blade coater, a lip coater, a Koma coater, a film coater or the like. It is formed by coating on a carrier film or a cover film and drying it. However, the film laminate is added with one, the weight-protecting agent, and the film of the welding material of the same material, and the film is formed by a long-lasting resistance. {Look-shaped light exposure of the film is exposed to the film or the core of the protective material before the line, the Μ / conformal base into the light film and the thin film of the IIV layer is the same as the agent on the agent Welding into the front load-carrying line resistance and. With the use of the film, the film can be brushed, and the layer can be coated with the release agent film layer. The thin film film and the like can be formed into a shape of a solderable dry thin machine, that is, the cover can be separated from the cover layer and peeled off, so that it can be used for the purpose of the lower case. EMBODIMENT The following examples and comparative examples are specifically described to illustrate the present invention, but the present invention is not limited by the following examples. In addition, the following "parts" and "%" are all based on -48- 201207555 unless otherwise stated. Synthesis Example 1 A novolac type cresol resin (produced by Showa Polymer Co., Ltd., trade name "SHONOL CRG951", OH equivalent) was fed into an autoclave equipped with a thermometer, a nitrogen gas introduction device, and an alkylene oxide introduction device and a stirring device. : 1 1 9 _ 4 ) 1 1 9 · 4 parts, potassium hydroxide 1 · 19 parts and toluene 1 19 · 4 parts, the system was replaced with nitrogen after stirring, and heated to heat. Subsequently, 63·8 parts of the epoxy propylene compound was slowly added dropwise, and the reaction was carried out at 125 to 132 ° C for 0 to 4.8 kg/cm 2 for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Propane reaction solution. It is an average of 1.08 moles of alkoxylated gas per phenol equivalent of a phenolic hydroxyl group. Next, 293.0 parts of the alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were fed with a stirrer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min, and reacted at 1 1 ° C for 12 hours while stirring. The water produced by the reaction distilled 1 2.6 parts of water in an azeotropic mixture with toluene. Subsequently, it was cooled to room temperature, and the resulting reaction solution was neutralized with 3 5.3 5 parts of a 15 % aqueous sodium hydroxide solution, followed by washing with water. Subsequently, the toluene was distilled off with 118 parts of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolac type acrylate resin solution. Then, '332 parts of the obtained novolac type acrylate resin solution and i.22 parts of triphenylphosphine were fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube at a rate of -49-201207555 10 ml/min. Air was blown in, and 60.8 parts of tetrahydrophthalic anhydride was gradually added thereto while stirring, and the mixture was reacted at 95 to 101 ° C for 6 hours. A resin solution of a photosensitive resin containing a carboxyl group having a solid content of 8811^1 <:011/8 and a nonvolatile content of 71% was obtained. Hereinafter, this is called paint A-1. Synthesis Example 2 A polycaprolactone diol as a polymer polyol (PLACCEL 208 manufactured by Daicel Chemical Industry Co., Ltd., molecular weight 830) 1,245 was fed into a 5 liter separable flask equipped with a thermometer, a stirrer, and a reflux condenser. Parts: 201 parts of dimethylolpropionic acid as a dihydroxy compound having a carboxyl group, 777 parts of isophorone diisocyanate as a polyisocyanate, and 2-hydroxyethyl acrylate as a (meth) acrylate having a hydroxyl group. Then, 0.5 part of p-methoxyphenol and di-tert-butylhydroxytoluene were separately injected. After heating to 60 ° C with stirring, the heating was stopped, and 0.8 parts of dibutyltin dilaurate was added. When the temperature in the reaction vessel begins to decrease, it is heated again, and stirring is continued at 80 ° C. The infrared absorption spectrum confirms that the absorption spectrum of the isocyanate group (2280 CHT1 ) disappears, and the reaction is terminated to obtain a viscous liquid urethane acrylate compound. . The carbitol acetate was adjusted to a nonvolatile content = 50% by mass. A resin solution of a solid component having an acid value of 47 mgKOH/g and a nonvolatile content of 50% of a carboxyl group-containing urethane (meth) acrylate compound was obtained. Hereinafter, this is called paint A-2. Synthesis Example 3 900 parts of diethylene glycol dimethyl ether as a solvent was added to a two-liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen-50-201207555 gas introduction tube, and as a polymerization. The third butylperoxy 2-ethylhexanoate of the initiator (manufactured by Nippon Oil & Fats Co., Ltd., trade name: PERBUTYL®) 21.4 parts was heated to 90 °C. After heating, 309.9 parts of methacrylic acid, 116.4 parts of methyl methacrylate, and 2-hydroxyethyl methacrylate (PLACCELFM1: manufactured by Daicel Chemical Industry Co., Ltd.) modified with lactone and 109.8 parts of a polymerization initiator Bis(4-tert-butylcyclohexyl)peroxydicarbonate (manufactured by Nippon Oil & Fats Co., Ltd., trade name; PEROYL TCP) 21.4 parts were added dropwise thereto within 3 hours, followed by ripening for 6 hours. This gave a copolymerized resin containing a carboxyl group. Further, the reaction was carried out under a nitrogen atmosphere. Next, 363.9 parts of 3,4-epoxycyclohexyl methacrylate (manufactured by Daicel Chemical Industry Co., Ltd., trade name; CYCLOMER A200), and 3.6 parts of dimethylbenzylamine as a ring-opening catalyst were used. Further, 1.80 parts of hydroquinone monomethyl ether as a polymerization inhibitor was added to a polymer resin containing a carboxyl group, and the mixture was heated to 100 ° C to carry out a ring-opening addition reaction of an epoxy group by stirring. After 16 hours, a resin solution having a solid content of 108.9 mgKOH/g, a weight average molecular weight of 25,000 and a solid content of 54% was obtained. Hereinafter, it is referred to as Paint A-3 Synthesis Example 4, and 650 parts of diethylene glycol monoethyl ether acetate is fed into o-cresol novolac-type epoxy resin (DIC (manufactured by DIC)' EPICLON N- 695 'softening point 95. (:, epoxy equivalent 214, average functional group number 7.6) 1070 parts (reduced 201207555 water glyceryl number (total aromatic ring): 5.0 moles), 360 parts of acrylic acid ( 5. 〇 Mo ear), and 1.5 parts of hydroquinone, heated and stirred until l ° ° C 'dissolved uniformly. Next, fed 3 3 parts of triphenylphosphine 'heated to 1 1 〇 ° C and reacted for 2 hours, then added triphenylphosphine 1.6 The temperature was raised to 120 ° C and the reaction was carried out for 12 hours. 525 parts of aromatic hydrocarbon (SOLVESSO 1 50 ) and 608 parts of tetrahydrophthalic anhydride (4.0 moles) were fed into the obtained reaction liquid. The reaction was carried out for 4 hours at ° C. Next, 142.0 parts (1.0 mol) of glycidyl methacrylate was fed to the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours to obtain a solid content acid value of 77 mgKOH/g, solid. 65% of the resin solution of the composition. Hereinafter referred to as paint R-1. Synthesis Example 5 in 200 parts of diethylene glycol monoethyl ether acetate O-cresol novolac-type epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6) 1 070 parts (glycidyl number (total number of aromatic rings) : 5.0 moles, 360 parts of acrylic acid (5.0 moles), and 1.5 parts of hydroquinone, heated and stirred to 100 ° C, and uniformly dissolved. Next, 4.3 parts of triphenylphosphine was fed, heated to 1 10 t and reacted for 2 hours. Thereafter, the temperature was raised to 120 ° C and the reaction was carried out for another 12 hours. In the obtained reaction liquid, 415 parts of aromatic hydrocarbons (SOLVESSO 150) and 45 6.0 parts of tetrahydrophthalic anhydride (3.0 moles) were fed, at 1 l〇. The reaction was carried out for 4 hours at ° C. After cooling, a resin solution having a solid content of 89 mg KOH/g and a solid content of 65% was obtained. Hereinafter, it was referred to as a paint R-2. • 52-201207555 Synthesis Example 6 Feeding A Phenolic novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C, epoxy equivalent 220) 2200 parts, 134 parts of dimethylolpropionic acid, 648.5 parts of acrylic acid, methyl hydrogen醌 4.6 parts, 1131 parts of carbitol acetate and 484.9 parts of Solvent naphtha, heated to 9.0 ° C and Mixing the reaction mixture was dissolved. Then, the reaction was cooled to 60 ° C, fed 13.8 parts of triphenylphosphine was heated to 100 ° C, about 32 hours reaction, an acid value of 0.5 mgKOH / g of reactants. Then, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate, and 58.8 parts of solvent oil were fed thereto, heated to 95 ° C, and reacted for about 6 hours, and cooled to obtain a solid content acid value of 40 mgKOH. / g, a resin solution of a photosensitive resin containing 65% of a carboxyl group. Hereinafter, it is referred to as paint R-3. Synthesis Example 7 400 parts of a bisphenol F type solid epoxy resin having an epoxy equivalent of 800 and a softening point of 79 ° C was dissolved in 925 parts of epichlorohydrin and 462.5 parts of dimethyl argon, and then stirred at 70 ° C under stirring. 98.5% of NaOH 8 1.2 parts were added over 100 minutes. After the addition, the reaction was carried out at 70 ° C for 3 hours. Next, the excess of the unreacted epichlorohydrin and the majority of the dimethyl hydrazine are distilled off under reduced pressure, and the reaction product containing the by-product salt and the dimethyl sulfite is dissolved in 750 parts of methyl isobutyl ketone, followed by addition. 10 parts of 30% NaOH, and reacted at 70 ° C for 1 hour. After the reaction was completed, the mixture was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled from the oil layer to obtain 370 parts of epoxy resin (a-1) having an epoxy equivalent of 290 and a softening point of 62 °C. Feeding the obtained epoxy resin (a-1) 2900 parts (10 equivalents), -53-201207555 acrylic acid 720 parts (l〇 equivalent), methylhydroquinone 2.8 parts, carbitol acetate 195 parts, The reaction mixture was dissolved by heating to 90 ° C 'with stirring'. Next, the reaction liquid was cooled to 60 ° C to feed 16.7 parts of triphenylphosphine, and heated to 1 Torr. (:, the reaction was carried out for about 32 hours, and an acid value of 1.〇11^1 (: 01^8 reactant) was obtained. Next, 786 parts of succinic anhydride (7·86 mol) and carbitol acetic acid were fed thereto. 423 parts of the ester was heated to 95 ° C, and the reaction was carried out for about 6 hours to obtain a resin solution having a solid content of 1 〇〇 mg KOH / g and a solid content of 65%. Hereinafter, it is referred to as lacquer R-4. ~13 and Comparative Examples 1 to 3 Using the resin solution of the above Synthesis Example, the ratios (mass parts) shown in Table 1 were prepared together with the various components shown in Table 1 below, and premixed with a stirrer to obtain three rolls. The mill was kneaded to prepare a photosensitive resin composition for a solder resist. Here, the particle size of the obtained photosensitive resin composition was measured by a particle size analyzer manufactured by ERIKSEN Co., Ltd. and evaluated to be 15 μm or less. - 201207555 [Table 1] Composition (parts by mass) . Degree of application ± m 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 A-1 141 141 141 141 141 141 141 \Ai dd 71 141 of δδ 141 A-2 6ΰ A-3 $6 Paint R-1 11 R-2 1b4 R-3 46 r-4 154 Also take (Β-1Γ1 IS ship 1 (B-3)·4 1.5 1.5 1.5 1.5 1.5 ii 1.5 1.S 1.S 1.5 1.5 1.6 \.b 1.5 1.5 HP-4032 *4 20 20 20 20 10 10 id iO 2ΰ ίύ Ο) 20 2Q VI^4700CA90,,:, 2ί 13 iSN355CA9(T. zi 13 T04PCA75,, ib - tortoise*β 0.3 0.3 ΰ.3 ΰ.3 0.3 0.3 0.3 0.3 ύ.3 0.5 0.3 0.3 0.3 oa ΰΛ 0.3 u 0.8 ύ.6 0.6 0.8 Od 0·δ ΰ.ό 0.8 ύ.6 0.6 0.8 ύ.8 0.6 ύ.ύ ύ.ύ U.tt phenothiazine Ot 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 2 2 2 2 2 2 2 2 2 B-33 *12 260 2όύ 200 ύόύό 2. 0 200 ίύύ 佥όο 2όύ 200 206 ίύό ίόό ίύο 200 ACTINYLAM*, J 25ΰ DHT-4A*m 5 5 S 5 5 5 S 5 S 5 SS 5 S b 5 Defoamer 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 A-dcp* , a 5 5 5 SS 5 S 5 δ 5 ί 5 5 5 S 5 DPHA • _ o 1S IS 15 a 15 15 1古IS 15 15 15 15 15 15 u> ii 1 PA-B80E*" 17.5 Mw-100LM"ie 12.5 ♦1 : 2-methyl-1-(4-methylthiophenyl)-2- Morpholinylpropan-1-one (IRGACURE 907: manufactured by Nippon Ciba) *2 : 2,4* diethylthioxanthone (1〇1^人01; 11£0孤-3: 曰本化薬Nor: 〉Company system) *3: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-yttrium-3-yl]-1,1-(0- IR 醯 ( (IRGACURE OXE 02: manufactured by Nippon Ciba) *4 : Naphthalene epoxy resin (made by DIC) »5: Naphthalene ring grease (made by DIC), HP-4700, carbitol Acid ester interception product 90%) »6: Naphthalene epoxy resin (made by Dongdu Chemical Co., Ltd.) ESN355 carbitol acetate extract 90% of individual components *7: Cresol novolac varnish epoxy resin化化成(股)) 704P card mustard acetic acid vinegar interception (solid content 75%) *8 : CI Pigment Blue 15:3 *9 : CI Pigment Yellow 147 *10 ·· 2-Silylbenzothiazole *11: Antioxidant (manufactured by Nippon Ciba Company) Note *12: Barium sulfate (manufactured by Nippon Chemical Industry Co., Ltd.) *13: Amine group of SILLITIN which is a compound composed of spherical silica sand and platy kiln Decane coupling Material processing product (manufactured by HOFFMANN MINERAL Co., Ltd.) *14 ··Hydrate talc (Kyowa Chemical Industry Co., Ltd.) *15: Diethylene sulphur monoethyl acetate vinegar *16: Dipentaerythritol hexaacrylate vinegar *17: lion isophthalic acid Ester (made by Asahi Kasei Chemicals Co., Ltd.) *18: Methylated trimeric amine resin (manufactured by Sanwa Chemical Co., Ltd.) Performance evaluation: <Optimum exposure amount> A circuit pattern substrate having a copper thickness of 18 μm is passed through a copper surface After roughening treatment (MEC ETCH BOND CZ-8100 manufactured by MEC), after washing with water and drying, the above-mentioned examples and comparative examples were fully coated by screen printing method -55-201207555 Photocuring thermosetting The resin composition is 80. (: The hot air circulating drying oven was dried for 60 minutes. After drying, exposure was carried out by using an exposure apparatus equipped with a high-pressure mercury lamp through a Step Tablet (Kodak No. 2) to perform development (30 ° C, 0.2 MPa, Lwt% sodium carbonate aqueous solution) The pattern of the step change pattern remaining at 60 seconds is the optimum exposure amount in the case of 7 stages. <Developability> The screen printing method is used to make the film thickness after drying to about 25 μm. The method of applying the photocurable thermosetting resin composition of the above examples and comparative examples to a bare copper substrate, and drying in a hot air circulating drying oven at 80 ° C for 30 minutes. After drying, it was 1 wt%. The sodium carbonate aqueous solution was subjected to development, and the time until the drying of the coating film was removed was measured by a stopwatch. <Maximum development lifetime> The composition of the above examples and comparative examples was completely coated on the screen to form a pattern by screen printing. On a copper foil substrate, it was dried at 80 ° C for 20 minutes to 80 minutes, and the substrate was taken out every 10 minutes, and allowed to cool to room temperature. The substrate was subjected to a pressure of 0.2 MP a at a pressure of 30 ° C of 1 wt% carbonic acid. The sodium aqueous solution was imaged for 60 seconds, with the most residue remaining. Allowable drying time as the maximum development life <contacting property> The composition of the foregoing examples and comparative examples was completely applied to the patterned copper foil substrate by screen printing, and the hot air circulation type at 80 ° C was used. Drying oven-56-201207555 Drying for 30 minutes' Let cool to room temperature. The negative film made of PET is brought into contact with the substrate, and HMW_GW2〇 manufactured by 〇RC company is pressed under reduced pressure for 1 minute 'subsequent' The column was evaluated for the state of film bonding when the negative film was peeled off. 〇: When the film was peeled off, there was no resistance at all, and no trace of the film remained. Δ: When the film was peeled off, it was only slightly blocked, and the film marks were small. X·· When peeling the film, Obstructed and clear film characteristics test: The composition of the foregoing examples and comparative examples were completely coated on the copper foil substrate of the pattern by screen printing, dried at 80 ° C for 30 minutes, and allowed to cool to the chamber. For the substrate, an exposure apparatus equipped with a high-pressure mercury lamp was used to expose the solder resist pattern with an optimum exposure amount, and a 1 wt% sodium carbonate aqueous solution at 30 ° C was used for development under the conditions of a spray pressure of 2 2 MPa. 90 seconds, get the photoresist pattern The substrate was irradiated with ultraviolet rays under the conditions of a cumulative exposure amount of 1000 mj/cm 2 by a UV transfer furnace, and then cured by heating at 150 ° C for 60 minutes. The obtained printed circuit board (evaluation substrate) was evaluated as follows. <Acid resistance > At room temperature, the evaluation substrate was immersed in a 10 v 〇l% H 2 SO 4 aqueous solution for 30 minutes, and the infiltration or coating film was visually confirmed to be eluted, and peeling was confirmed by tape peeling. 〇: No change was confirmed Δ: only a slight change -57-201207555 X: Swelling and peeling caused by coating film expansion <Alkaline resistance> The evaluation substrate was immersed in a 10 vol% aqueous NaOH solution for 30 minutes at room temperature to visually confirm the dissolution of the infiltration or coating film, and then Peeling was confirmed by tape peeling. 〇: It is confirmed that there is no change Δ: only a slight change X: swelling of the film caused by swelling of the film < solder heat resistance> The evaluation substrate coated with the rosin-based flux is immersed in a solder bath set at 260 ° C in advance After the flux was washed with the modified alcohol, the expansion/peeling of the photoresist layer was visually evaluated. The judgment criteria are as follows. 〇: 3 or more times of immersion for 10 seconds, no peeling was observed. Δ: 3 times of immersion for 10 seconds, a little peeling, X: immersion within 3 times, 10 seconds after the photoresist layer was expanded, peeled < Electrolytic gold plating> Electroless nickel plating bath and electroless gold plating bath using a commercially available product were electroplated under the conditions of nickel 5 μm, gold ruthenium 〇 5 μm, and the resist layer was peeled off by tape peeling, and After the plating was infiltrated, the resist layer was peeled off by tape peeling. The judgment criteria are as follows. 〇: After electroplating, it was confirmed that there was only a little infiltration' but no peeling after peeling off the tape-58-201207555 △: It was confirmed that only a little infiltration was observed after plating, and peeling X was also found after peeling of the tape: peeling after plating < pc τ resistance> The evaluation substrate on which the solder resist hardening coating film was formed was treated at 121 ° C, saturated, and 0.2 MPa for 168 hours using a PCT apparatus (HAST SYSTEM TPC-412MD manufactured by ESPEC Co., Ltd.), and the state of the coating film was evaluated. The judgment criteria are as follows. 〇: no swelling, peeling, discoloration, dissolution △: only a little swelling, peeling, discoloration, dissolution X: multiple expansion, peeling, discoloration, dissolution & cold heat shock resistance > The evaluation substrate of the solder resist hardening film of the 〇 pattern. The obtained evaluation substrate was subjected to a thermal shock tester (manufactured by ETAC) at -55 ° C / 30 minutes to 150 ° C / 30 minutes as a cycle, and subjected to a resistance test of 1,000 cycles. After the test, the cured film after the treatment was visually observed, and the occurrence of cracks was judged based on the following criteria. 〇: The cracking rate is less than 30% △: The cracking rate is 30 to 50% X: The cracking rate is over 50% <HAST characteristics> -59- 201207555 The comb-shaped electrode is formed (line/space=50 A solder resist hardening coating film was formed on the BT substrate of μm/50 μm to prepare an evaluation substrate. The evaluation substrate was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, charged at a voltage of 12 V, and subjected to a HAST test in the tank for 168 hours. The insulation resistance 槽 in the tank after 1 68 hours was evaluated according to the following judgment criteria. 〇: more than 108 Ω Δ : 106 to 108 Ω X : less than 1 〇 6 Ω The results of the above evaluation tests are shown in Table 2 below. 【Table 2】
特性 货施例 比較例 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 最適曝光量 (mJ/cm2) 400 150 150 150 150 150 150 150 130 150 150 150 150 ISO 150 130 顯像性(秒) 35 36 33 34 29 28 30 26 34 33 34 36 36 31 35 47 最大顯像镜 命(分鐘) 70 60 60 60 60 60 60 60 60 60 60 60 60 60 60 40 龜裂性 Δ △ △ Δ Δ Δ △ Δ △ △ △ 〇 〇 Δ 〇 △ 耐酸性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 焊料耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐無電解鍍 金性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ 〇 PCT耐性 0 〇 〇 〇 △ 〇 〇 〇 〇 〇 厶 〇 〇 〇 X X 冷熱衝擊耐 性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ △ A HAST特性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Δ 〇 〇 〇 X X 特性試驗 以網版印刷將前述實施例1 3及比較例1之組成物全面 塗佈於形成有圖型之銅箔基板上’在8〇 °C乾燥30分鐘’放 冷至室溫。對該基板上,使用搭載高壓水銀燈之曝光裝置 ,以最適曝光量使阻焊劑圖型曝光,以3〇°C之lwt%碳酸鈉 -60- 201207555 水溶液在噴霧壓力0.2 MPa之條件下進行顯像90秒,獲得阻 劑圖型,分別爲實施例I4及比較例4。使該基板在UV輸送 帶爐中,於累積曝光量1 000 mJ/cm2之條件經紫外線照射 後,在 130°C、140°C 、150°C、160°C、17〇°C 、180。(:或 1 9(TC加熱60分鐘而硬化》對所得印刷基板(評價基板) 如下述評價其特性。結果示於表3及表4。 <Tg測定> 以 Seiko instrument公司製造之 TMA6100,邊對 3mmx 10mm尺寸之硬化皮膜施加10g之荷重,邊以一定之升溫速 度,在0°C ~26(TC之溫度範圍內進行拉伸試驗,計算外插 點以計算出玻璃轉移溫度Tg » <CTE測定> 以 Seiko instrument公司製造之 TMA6100,邊對 3mmx 10mm尺寸之硬化皮膜施加10g之荷重,邊以一定之升溫速 度,在0°C〜26(TC之溫度範圍內進行拉伸試驗。由對於溫 度之硬化皮膜伸長量計算出線熱膨脹係數CTE。 【表3】 特性 實施例1 < 硬》g 130°C 140°C 150°C 160°C 170°C 180°C 190°C 焊料耐熱性 〇 〇 〇 Ο Ο 〇 〇 耐無電解 鍍金性 〇 〇 〇 〇 〇 〇 Ο PCT耐性 Ο 〇 〇 〇 〇 〇 ο 冷熱衝擊耐性 〇 〇 Ο 〇 Ο 〇 〇 HAST特性 〇 〇 Ο 〇 〇 〇 ο Tg(°C) 125 126 124 125 125 124 127 CTE (ppm) 36 35 36 36 34 34 35 201207555 【表4】 特性 比較例4 硬化溫度 130°C 140°C 150°C 160°C 170°C 180°C 190°C 焊料耐熱性 Δ Ο 〇 0 Ο 〇 〇 耐無電解 鍍金性 X 〇 0 0 Δ Δ X PCT耐性 X X ο 〇 Δ △. Δ 冷熱衝擊耐性 Δ Δ Δ Δ Δ X X HAST特性 X Δ ο ο ο Δ Δ Tg(°C) 90 95 100 115 120 125 130 CTE (ppm) 65 57 55 55 50 45 40 實施例15〜22及比較例5~7 以甲基乙基酮稀釋以表1中所示之調配比例調製而成 之實施例1、3、4、6、7、8、9、11及比較例1、2、3之各 組成物,塗佈在PET薄膜上且在80°C乾燥30分鐘,形成厚 2 0μηι之感光性樹脂組成物層。進而於其上貼合覆蓋薄膜製 作乾膜,分別爲實施例15~22、比較例5〜7。 <乾膜評價> 自如上述獲得之乾膜剝離覆蓋薄膜,在形成圖型之銅 箔基板上熱層合薄膜,接著,在與前述實施例之塗膜特性 評價中所用基板相同之條件下曝光。曝光後剝離載體薄膜 ,以30°C之lwt%碳酸鈉水溶液在噴佈壓力0.2MPa之條件 下進行顯像90秒,獲得阻劑圖型。該基板以UV輸送帶爐 ,在累積曝光量1 000 mJ/cm2之條件下經紫外線照射後, 以l5〇°C加熱60分鐘硬化。針對具有所得硬化皮膜之試驗 基板’以前述試驗方法及評價方法,進行各特性之評價試 驗。結果不於表5。 -62- 201207555Characteristic Goods Comparative Example 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 Optimum exposure (mJ/cm2) 400 150 150 150 150 150 150 150 130 150 150 150 150 ISO 150 130 Imaging ( Seconds) 35 36 33 34 29 28 30 26 34 33 34 36 36 31 35 47 Maximum mirror life (minutes) 70 60 60 60 60 60 60 60 60 60 60 60 60 60 60 40 Cracking Δ △ Δ Δ Δ Δ △ Δ △ △ △ 〇〇 Δ 〇 △ acid resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 alkali resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇 solder heat resistance Sex resistance to electroless gold plating 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 △ 〇 PCT resistance 0 〇〇〇 △ 〇〇〇〇〇厶〇〇〇XX Thermal shock resistance 〇〇〇〇〇〇〇〇〇〇〇〇〇△ △ A HAST characteristic 〇〇〇〇〇〇〇〇〇〇Δ 〇〇〇 XX characteristic test The above implementation is carried out by screen printing The composition of Example 1 3 and Comparative Example 1 was completely coated on On the copper foil substrate on which the pattern was formed, it was allowed to 'dry at 8 ° C for 30 minutes' and allowed to cool to room temperature. On the substrate, an exposure apparatus equipped with a high-pressure mercury lamp was used to expose the solder resist pattern with an optimum exposure amount, and the image was developed at a spray pressure of 0.2 MPa with a 1 wt% sodium carbonate-60-201207555 aqueous solution at 3 °C. At 90 seconds, a resist pattern was obtained, which was Example I4 and Comparative Example 4, respectively. The substrate was irradiated with ultraviolet rays under conditions of an accumulated exposure amount of 1 000 mJ/cm 2 in a UV conveyor belt furnace at 130 ° C, 140 ° C, 150 ° C, 160 ° C, 17 ° C, and 180 °. (: or 19 (the TC was heated for 60 minutes and hardened) The obtained printed circuit board (evaluation substrate) was evaluated for its characteristics as follows. The results are shown in Tables 3 and 4. [Tg measurement> TMA6100 manufactured by Seiko Instrument Co., Ltd., Apply a load of 10g to a hardened film of 3mm x 10mm size, and perform a tensile test at a temperature rise rate of 0 °C ~ 26 (TC) at a certain temperature rise rate, calculate the extrapolation point to calculate the glass transition temperature Tg » < CTE measurement> A TMA 6100 manufactured by Seiko Instrument Co., Ltd. was subjected to a tensile test at a temperature rise of 0 ° C to 26 (TC) while applying a load of 10 g to a hardened film of 3 mm x 10 mm size. The linear thermal expansion coefficient CTE was calculated from the elongation of the hardened film for temperature. [Table 3] Characteristic Example 1 < Hard" g 130 ° C 140 ° C 150 ° C 160 ° C 170 ° C 180 ° C 190 ° C Solder Heat resistance 〇〇〇Ο 〇〇 无 resistance to electroless gold plating PCT PCT resistance Ο 〇〇〇〇〇ο Thermal shock resistance 〇〇Ο 〇〇 AST HAST characteristics 〇〇Ο 〇〇〇ο Tg (°C) 125 126 124 125 125 124 127 CTE (ppm) 36 35 36 36 34 34 35 201207555 [Table 4] Characteristic comparison example 4 Hardening temperature 130 ° C 140 ° C 150 ° C 160 ° C 170 ° C 180 ° C 190 ° C Solder heat resistance Δ Ο 〇0 Ο 〇〇 resistance to electroless gold plating X 〇0 0 Δ Δ X PCT resistance XX ο 〇 Δ Δ. Δ Thermal shock resistance Δ Δ Δ Δ Δ XX HAST characteristic X Δ ο ο ο Δ Δ Tg (°C 90 95 100 115 120 125 130 CTE (ppm) 65 57 55 55 50 45 40 Examples 15 to 22 and Comparative Examples 5 to 7 were prepared by diluting with methyl ethyl ketone in the proportions shown in Table 1. Each of the compositions of Examples 1, 3, 4, 6, 7, 8, 9, 11 and Comparative Examples 1, 2, and 3 was coated on a PET film and dried at 80 ° C for 30 minutes to form a thickness of 20 μm The photosensitive resin composition layer was further bonded to the cover film to form a dry film, which were Examples 15 to 22 and Comparative Examples 5 to 7, respectively. <Dry Film Evaluation> The dry film release coating film obtained as described above was used. The film was thermally laminated on the copper foil substrate on which the pattern was formed, and then exposed under the same conditions as those used in the evaluation of the film properties of the foregoing examples. After the exposure, the carrier film was peeled off, and development was carried out for 90 seconds at a spray pressure of 0.2 MPa at a temperature of 0.2 MPa at a spray temperature of 30 ° C to obtain a resist pattern. The substrate was cured by UV irradiation at a cumulative exposure of 1 000 mJ/cm 2 and then heated at 15 ° C for 60 minutes in a UV conveyor belt furnace. The evaluation test of each characteristic was carried out for the test substrate having the obtained hardened film by the above test method and evaluation method. The results are not shown in Table 5. -62- 201207555
【表5】 特性 實方 m 比較例 15 16 17 18 19 20 21 22 5 6 7 最適曝光量 (m J/cm2) 400 150 150 150 150 150 130 150 150 150 130 顯像性渺) 37 36 36 31 33 29 37 36 33 37 50 耐酸性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐鹼性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 焊料耐熱性 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 耐無電解 齡性 〇 〇 〇 〇 〇 〇 〇 〇 〇 Δ 0 PCT耐性 〇 〇 〇 〇 〇 〇 〇 △ 〇 X X 冷熱衝擊耐性 〇 〇 〇 〇 〇 〇 〇 〇 Δ Δ Δ HAST特性 〇 〇 〇 〇 〇 〇 〇 △ 〇 X X <乾膜評價> 自使用前述實施例1及比較例1之組成物之如上述獲得 之乾膜剝離覆蓋薄膜,在形成圖型之銅箔基板上熱層合薄 膜,接著,在與前述實施例之塗膜特性評價中所用基板相 同之條件曝光。曝光後,剝離載體薄膜,以30°c之lwt%碳 酸鈉水溶液在噴佈壓力0.2MPa之條件進行顯像90秒,獲得 阻劑圖型’分別爲實施例23及比較例8。該基板以UV輸送 帶爐,在累積曝光量1 000 mJ/cm2之條件下經紫外線照射 後’以 130°C 、140°C、15(TC、1601、17〇。(: 、180°C 或 190 °C加熱60分鐘而硬化。針對具有所得硬化皮膜之試驗 基板,以前述試驗方法及評價方法,進行各特性之評價試 驗。結果示於表6及表7。 -63- 201207555 【表6】 特性 資施例2 3 硬化謎 130°C 140°C 150°C 160°C 170°C 180°C 190°C 焊料耐熱性 〇 〇 〇 〇 〇 〇 〇 耐無電解 鍍金性 〇 〇 〇 〇 〇 o o PCT耐性 〇 〇 〇 〇 〇 〇 〇 冷熱衝擊耐性 〇 0 〇 〇 〇 〇 o HAST特性 〇 〇 〇 〇 〇 〇 o Tg(°C) 125 126 124 125 125 124 127 CTE (ppm) 21 21 22 21 22 22 22 【表7】 特性 比較例8 硬化激 130°C 140°C 1 50°C 160°C 170°C 180°C 190°C 焊料耐熱性 Δ Ο 〇 〇 〇 〇 〇 耐無電解 鍍金性 X 〇 〇 〇 Δ Δ X PCT耐性 X X 〇 〇 Δ Δ Δ 冷熱衝擊耐性 Δ Δ Δ Δ Δ X X HAST特性 X Δ 〇 〇 Δ Δ Δ Tg(°C) 91 95 107 118 128 129 135 CTE (ppm) 65 60 57 55 49 41 39 由前述表6及表7所示結果可清楚了解’本發明之光硬 化性熱硬化性樹脂組成物確認可使用作爲兼具有對於半導 體封裝用阻焊劑所必需之PCT耐性、冷熱衝擊耐性、HAST 特性(電特性)之光硬化性熱硬化性樹脂組成物。 [產業上之可能利用性] 藉由使用本發明之光硬化性熱硬化性樹脂組成物,可 形成PCT耐性、HAST耐性、無電解鍍金耐性、耐熱性等優 異之硬化皮膜,故可較好地使用於形成印刷配線板或可撓 性配線板等之阻焊劑,尤其是半導體封裝用阻焊劑。 -64-[Table 5] Characteristic square m Comparative example 15 16 17 18 19 20 21 22 5 6 7 Optimum exposure amount (m J/cm 2 ) 400 150 150 150 150 150 130 150 150 150 130 Development 渺) 37 36 36 31 33 29 37 36 33 37 50 Acid resistance, alkali resistance, solder heat resistance, resistance Electrolytic age 〇〇〇〇〇〇〇〇〇Δ 0 PCT resistance 〇〇〇〇〇〇〇△ 〇XX Thermal shock resistance 〇〇〇〇〇〇〇〇Δ Δ Δ HAST characteristic 〇〇〇〇〇〇〇△ 〇XX <dry film evaluation> The dry film peeling cover film obtained as described above using the composition of the above-mentioned Example 1 and Comparative Example 1 was thermally laminated on the copper foil substrate on which the pattern was formed, and then, The conditions were the same as those of the substrate used in the evaluation of the coating film characteristics of the foregoing examples. After the exposure, the carrier film was peeled off, and development was carried out for 90 seconds under a condition of a spray pressure of 0.2 MPa at 30 ° C of a 1 wt% aqueous sodium carbonate solution, and the resist pattern was obtained as Example 23 and Comparative Example 8, respectively. The substrate is in a UV conveyor belt furnace, and after irradiation with ultraviolet rays under the condition of an accumulated exposure amount of 1 000 mJ/cm 2 'at 130 ° C, 140 ° C, 15 (TC, 1601, 17 〇. (:, 180 ° C or The test was performed by heating at 190 ° C for 60 minutes. The test of each of the properties of the test substrate having the obtained hardened film was carried out by the above test method and evaluation method. The results are shown in Tables 6 and 7. -63 - 201207555 [Table 6] Features 2 2 Hardening mystery 130°C 140°C 150°C 160°C 170°C 180°C 190°C Solder heat resistance 无Resistant to electroless gold plating oo PCT resistance, thermal shock resistance, 〇0 〇〇〇〇o HAST characteristics 〇〇〇〇〇〇o Tg(°C) 125 126 124 125 125 124 127 CTE (ppm) 21 21 22 21 22 22 22 [Table 7] Characteristic comparison example 8 Hardening stress 130 ° C 140 ° C 1 50 ° C 160 ° C 170 ° C 180 ° C 190 ° C solder heat resistance Δ 〇〇〇〇〇 〇〇〇〇〇 resistance to electroless gold plating X 〇 〇〇Δ Δ X PCT resistance XX 〇〇Δ Δ Δ Thermal shock resistance Δ Δ Δ Δ Δ XX HAST characteristics X Δ 〇〇 Δ Δ Δ Tg (°C) 91 95 107 118 128 129 135 CTE (ppm) 65 60 57 55 49 41 39 From the results shown in Tables 6 and 7 above, the light curability of the present invention is clearly understood. In the thermosetting resin composition, it is confirmed that a photocurable thermosetting resin composition which has both PCT resistance, thermal shock resistance, and HAST characteristics (electrical characteristics) necessary for a solder resist for semiconductor encapsulation can be used. Possible use] By using the photocurable thermosetting resin composition of the present invention, a cured film excellent in PCT resistance, HAST resistance, electroless gold plating resistance, heat resistance, and the like can be formed, so that it can be preferably used for forming printing. Solder resists such as wiring boards or flexible wiring boards, especially solder resists for semiconductor packages. -64-