TWI838715B

TWI838715B - Photosensitive resin composition with improved system color stability, photosensitive resin laminate containing the same and use thereof

Info

Publication number: TWI838715B
Application number: TW111110774A
Authority: TW
Inventors: 嚴春霞
Original assignee: 大陸商常州正潔智造科技有限公司
Priority date: 2021-03-26
Filing date: 2022-03-23
Publication date: 2024-04-11

Abstract

本發明公開一種具有提升的體系色相穩定性的感光性樹脂組合物，包含下列組分：(A)2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑，結構如式(I)所示，其中具有1-4’連接位的式(Ⅱ)化合物和具有1-5’連接位的式(Ⅲ)化合物的含量之和佔該混合光引發劑的3%以下；(B)鹼可溶性聚合物；(C)具有烯屬不飽和雙鍵的化合物；(D)供氫體；(E)任選的其它助劑。本發明的感光性樹脂組合物及其乾膜具有優異的分辨率和色相穩定性，在-20-40℃長時間儲存後也不會有分辨率下降的趨勢，在製造印刷電路板、保護圖案、導體圖案、引框線、半導體封裝等方面具有廣泛應用。 The present invention discloses a photosensitive resin composition with improved system hue stability, comprising the following components: (A) a 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator, the structure of which is shown in formula (I), wherein the sum of the contents of the compound of formula (II) having a 1-4' connecting position and the compound of formula (III) having a 1-5' connecting position accounts for less than 3% of the mixed photoinitiator; (B) an alkali-soluble polymer; (C) a compound having an olefinic unsaturated double bond; (D) a hydrogen donor; and (E) other optional additives. The photosensitive resin composition and its dry film of the present invention have excellent resolution and color stability, and there is no tendency of resolution reduction after long-term storage at -20-40°C. It has a wide range of applications in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc.

Description

具有提升的體系色相穩定性的感光性樹脂組合物、包含其的感光性樹脂層疊體及其用途 Photosensitive resin composition with improved system color stability, photosensitive resin layer stack containing the same and its use

本發明屬於光固化技術領域，具體涉及一種具有提升的體系色相穩定性的感光性樹脂組合物及其應用。 The present invention belongs to the field of photocuring technology, and specifically relates to a photosensitive resin composition with improved system hue stability and its application.

近年來隨著個人電腦等精密電子設備上所使用的印刷線路板的微小化，使得具有高感光度、高解像性及分辨率的感光性樹脂組合物成為研究的熱點。而光引發劑作為感光性樹脂組合物中必不可少的組分之一，要求其具有高的引發效率、與體系具有較好的相容性和優異的溶解性等優異性能。六芳基雙咪唑(HABI)類化合物具有特殊的化學結構，在紫外光作用下可以光解產生大分子自由基，是光固化領域特別是自由基聚合領域非常重要的一類光引發劑。 In recent years, with the miniaturization of printed circuit boards used in precision electronic devices such as personal computers, photosensitive resin compositions with high sensitivity, high resolution and resolution have become a hot topic of research. As one of the essential components in photosensitive resin compositions, photoinitiators are required to have excellent properties such as high initiation efficiency, good compatibility with the system and excellent solubility. Hexaarylbiimidazole (HABI) compounds have a special chemical structure and can photolyze to produce macromolecular free radicals under the action of ultraviolet light. They are a very important type of photoinitiator in the field of photocuring, especially in the field of free radical polymerization.

在HABI類光引發劑中，2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑(BCIM)應用最為廣泛。BCIM存在多種連接位的異構體，現有市場的BCIM基本上是由多種連接位的異構體混合而成。目前已報導的BCIM在感光性樹脂組合物中的應用均未對內部異構體組成和含量做進一步要求，僅是將BCIM混合物直接應用於組合物中。但是一方面，市場上不同廠家生產的BCIM應用性能差異較大，給下游生產廠家帶來很大的困惑；另一方面，含有現有BCIM產品的感光性樹脂組合物及其乾膜色相穩定性低，長時間保存時存在顯色異常的問題，易導致製品不良，是亟需解決的一個難題。 Among HABI photoinitiators, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (BCIM) is the most widely used. BCIM has multiple isomers at the connecting position, and the BCIM currently available on the market is basically a mixture of multiple isomers at the connecting position. The applications of BCIM in photosensitive resin compositions reported so far have not made further requirements on the composition and content of internal isomers, but simply directly applied the BCIM mixture to the composition. However, on the one hand, the application performance of BCIM produced by different manufacturers in the market varies greatly, which brings great confusion to downstream manufacturers; on the other hand, the photosensitive resin composition containing existing BCIM products and its dry film have low color stability and abnormal color development when stored for a long time, which can easily lead to defective products. This is a difficult problem that needs to be solved urgently.

申請人的研發團隊在研究2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑的過程中發現，不同連接位的BCIM異構體和含量對感光性樹脂組合物及其乾膜的性能有明顯影響。因此，探究異構體的結構和含量對BCIM混合光引發劑性能的影響是進一步提高BCIM實際應用性能的一種有效手段。 The applicant's R&D team found in the process of studying 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole that the BCIM isomers and contents at different connection positions have a significant effect on the performance of the photosensitive resin composition and its dry film. Therefore, exploring the effect of the structure and content of the isomers on the performance of the BCIM mixed photoinitiator is an effective means to further improve the practical application performance of BCIM.

針對現有技術發展的需求，本發明的目的主要在於提供一種具有提升的體系色相穩定性的感光性樹脂組合物，該組合物及其乾膜具有優異的分辨率和色相穩定性，在-20-40℃長時間儲存後也不會有分辨率下降的趨勢。 In response to the needs of existing technology development, the main purpose of the present invention is to provide a photosensitive resin composition with improved system hue stability. The composition and its dry film have excellent resolution and hue stability, and there is no tendency of resolution reduction after long-term storage at -20-40°C.

為了實現上述目的，採用的具體技術方案如下。 In order to achieve the above purpose, the specific technical solutions adopted are as follows.

一種具有提升的體系色相穩定性的感光性樹脂組合物，包含下列組分：(A)2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑，結構如式(I)所示，

A photosensitive resin composition with improved system color stability comprises the following components: (A) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator, the structure of which is shown in formula (I),

其中，具有1-4’連接位的式(II)化合物和具有1-5’連接位的式(III)化合物的含量之和佔該混合光引發劑的3%以下， Wherein, the sum of the contents of the compound of formula (II) having a 1-4' linking position and the compound of formula (III) having a 1-5' linking position accounts for less than 3% of the mixed photoinitiator,

(B)鹼可溶性聚合物； (B) Alkali soluble polymers;

(C)具有烯屬不飽和雙鍵的化合物； (C) Compounds having olefinic unsaturated double bonds;

(D)供氫體； (D) Hydrogen donor;

(E)任選地(optionally)，其它助劑。 (E) Optionally, other additives.

本發明的另一個目的在於提供上述感光性樹脂組成物及其乾膜在製造印刷電路板、保護圖案、導體圖案、引框線、半導體封裝等方面中的應用。 Another object of the present invention is to provide the application of the above-mentioned photosensitive resin composition and its dry film in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc.

基於本發明的目的，以下對本發明的感光性樹脂組合物及其應用的各方面進行更詳細的說明。 Based on the purpose of the present invention, the photosensitive resin composition of the present invention and various aspects of its application are described in more detail below.

<感光性樹脂組合物><Photosensitive resin composition>

2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑(A) 2,2’-Bis(o-chlorophenyl)-4,4’,5,5’-tetraphenylbiimidazole mixed photoinitiator (A)

本發明的2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑，結構如式(I)所示， The 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator of the present invention has a structure as shown in formula (I),

除非另有說明，這裡所說的百分比是指質量百分比。 Unless otherwise stated, the percentages mentioned here refer to mass percentages.

進一步地，式(II)和(III)兩種化合物的含量之和佔該混合光引發劑的1%以下。 Furthermore, the sum of the contents of the two compounds of formula (II) and (III) accounts for less than 1% of the mixed photoinitiator.

本發明的2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑中，具有1-2’連接位的式(IV)化合物和具有2’-3連接位的式(V)化合物佔主體，兩種化合物的含量之和佔該混合光引發劑的96%以上， In the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention, the compound of formula (IV) having a 1-2' connection position and the compound of formula (V) having a 2'-3 connection position are the main components, and the sum of the contents of the two compounds accounts for more than 96% of the mixed photoinitiator.

除了上述式(II)、(III)、(IV)、(V)四種化合物之外，任選地，本發明的2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑(BCIM)中還可含有少量3-4’、3-5’、1-1’、1-3’、3-3’等連接位的異構體。 In addition to the above-mentioned four compounds of formula (II), (III), (IV), and (V), optionally, the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator (BCIM) of the present invention may also contain a small amount of isomers of the connection positions such as 3-4', 3-5', 1-1', 1-3', and 3-3'.

本發明的2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑對其中式(II)化合物和式(III)化合物兩者之間的比例沒有特別限定，對式(IV)化合物和式(V)化合物兩者之間的比例也沒有特別限定，只要兩者含量之和滿足前述要求即可達到本發明的目的。本文中，2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基二咪唑混合光引發劑中的組分含量由高效液相色譜儀檢測。 The 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator of the present invention has no special restrictions on the ratio between the compound of formula (II) and the compound of formula (III), and there is no special restrictions on the ratio between the compound of formula (IV) and the compound of formula (V). As long as the sum of the contents of the two meets the above requirements, the purpose of the present invention can be achieved. In this article, the component content in the 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole mixed photoinitiator is detected by high performance liquid chromatography.

BCIM是光刻膠領域公知的一類光引發劑，可通過取代三苯基咪唑類化合物的氧化偶合來製備，製備中所用的氧化劑可以舉例如次氯酸鈉、鐵氰化鉀等，所用相轉移催化劑可以舉例如四丁基溴化銨、苄基三乙基氯化銨、冠醚(15-冠醚-5、18-冠醚-6)、聚乙二醇等，具體製備工藝可參照例如US3784557、US4622286和US4311783等現有技術中的記載(在此將其全文引入以作為參考)。通過現有製備工藝得到的BCIM中，上述式(II)和(III)兩種化合物的含量之和佔BCIM混合光引發劑的含量偏高。 BCIM is a type of photoinitiator known in the field of photoresist, which can be prepared by oxidative coupling of substituted triphenylimidazole compounds. The oxidants used in the preparation can be, for example, sodium hypochlorite, potassium ferric cyanide, etc. The phase transfer catalysts used can be, for example, tetrabutylammonium bromide, benzyltriethylammonium chloride, crown ethers (15-crown-5, 18-crown-6), polyethylene glycol, etc. The specific preparation process can refer to the records in the prior art such as US3784557, US4622286 and US4311783 (the full text of which is hereby introduced as a reference). In the BCIM obtained by the existing preparation process, the sum of the contents of the above-mentioned two compounds of formula (II) and (III) accounts for a relatively high content of the BCIM mixed photoinitiator.

本發明在現有工藝的基礎上，對產物進行溶劑打漿和重結晶工藝，即可方便地獲得滿足本發明組成要求的BCIM混合光引發劑。所述溶劑可以是甲苯、苯、甲醇、乙醇、乙酸乙酯、二氯甲烷、水中的一種或兩種以上的組合物。 Based on the existing process, the present invention conducts solvent slurrying and recrystallization process on the product to conveniently obtain the BCIM mixed photoinitiator that meets the composition requirements of the present invention. The solvent can be one or a combination of two or more of toluene, benzene, methanol, ethanol, ethyl acetate, dichloromethane, and water.

在100質量份的感光性樹脂組合物中，BCIM混合光引發劑的含量較佳為1-10質量份。此含量範圍內，BCIM混合光引發劑在表現出優異感光活性和分辨率的同時，能夠帶來更好的色相穩定性。 In 100 parts by weight of the photosensitive resin composition, the content of the BCIM mixed photoinitiator is preferably 1-10 parts by weight. Within this content range, the BCIM mixed photoinitiator can bring better hue stability while showing excellent photosensitivity and resolution.

鹼可溶性聚合物(B) Alkaline soluble polymer (B)

鹼可溶性聚合物可賦予感光性樹脂組合物成膜功能。作為鹼可溶性聚合物，只要是具有這樣特性的聚合物就可以沒有特別限制地適用。 Alkali-soluble polymers can impart film-forming properties to photosensitive resin compositions. As alkali-soluble polymers, any polymer having such properties can be used without particular limitation.

示例性地，適用的鹼可溶性聚合物可以是(甲基)丙烯酸系聚合物、苯乙烯系聚合物、環氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、醯胺系樹脂、醯胺環氧系樹脂、醇酸系樹脂以及酚醛系樹脂等。 For example, the applicable alkali-soluble polymer may be (meth) acrylic polymer, styrene polymer, epoxy polymer, aliphatic polyurethane (meth) acrylate polymer, aromatic polyurethane (meth) acrylate polymer, amide resin, amide epoxy resin, alkyd resin, phenolic resin, etc.

進一步地，鹼可溶性聚合物可經由聚合性單體進行自由基聚合而得到。作為聚合性單體，可例舉出：苯乙烯、乙烯基甲苯、α-甲基苯乙烯、對甲基苯乙烯、對乙基苯乙烯、對氯苯乙烯等在α-位或在芳香族環上被取代的可聚合的苯乙烯衍生物；丙烯醯胺、雙丙酮丙烯醯胺等丙烯醯胺衍生物；丙烯腈、乙烯基正丁基醚等乙烯基醇的醚類衍生物；(甲基)丙烯酸、α-溴代(甲基)丙烯酸、α-氯代(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸、β-苯乙烯基(甲基)丙烯酸等(甲基)丙烯酸衍生物；(甲基)丙烯酸烷基酯、(甲基)丙烯酸苄酯、甲基丙烯酸苯氧基乙酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸縮水甘油酯、2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基)丙烯酸酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸二甲基氨基乙酯、(甲基)丙烯酸二乙基氨基乙酯、(甲基)丙烯酸縮水甘油酯等(甲基)丙烯酸酯類化合物；馬來酸、馬來酸酐、馬來酸單甲酯、馬來酸單乙酯、馬來酸單異丙酯等馬來酸單酯；富馬酸、肉桂酸、α-氰基肉桂酸、衣康酸、巴豆酸、丙醇酸、N-乙烯基己內醯胺；N-乙烯基吡咯烷酮等。這些聚合性單體可以單獨使用，也可以兩種以上組合使用。 Furthermore, the alkali-soluble polymer can be obtained by free radical polymerization of polymerizable monomers. Examples of polymerizable monomers include: polymerizable styrene derivatives substituted at the α-position or on the aromatic ring, such as styrene, vinyl toluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, and p-chlorostyrene; acrylamide derivatives such as acrylamide and diacetone acrylamide; ether derivatives of vinyl alcohol such as acrylonitrile and vinyl n-butyl ether; (meth)acrylic acid derivatives such as (meth)acrylic acid, α-bromo(meth)acrylic acid, α-chloro(meth)acrylic acid, β-furanyl(meth)acrylic acid, and β-styryl(meth)acrylic acid; alkyl(meth)acrylates, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, and (meth)acrylic acid. (Meth)acrylate compounds such as dimethylaminoethyl ester, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate; maleic acid monoesters such as maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propionic acid, N-vinylcaprolactam; N-vinylpyrrolidone, etc. These polymerizable monomers can be used alone or in combination of two or more.

進一步地，從鹼顯影性和密合性的角度考慮，較佳使用含羧基的鹼可溶性聚合物。具有羧基的鹼可溶性聚合物可以為包含(甲基)丙烯酸作為單體單元的丙烯酸樹脂，其通過使用(甲基)丙烯酸作為單體單元導入羧基；可以為除(甲基)丙烯酸以外進一步包含(甲基)丙烯酸烷基酯作為單體單元的共聚物；也可以為除(甲基)丙烯酸以外進一步含有除(甲基)丙烯酸和(甲基)丙烯酸烷基酯以外的聚合性單體(如具有乙烯性不飽和基團的單體)作為單體成分的共聚物。 Furthermore, from the perspective of alkali developing property and adhesion, it is preferable to use an alkali-soluble polymer containing a carboxyl group. The alkali-soluble polymer having a carboxyl group may be an acrylic resin containing (meth)acrylic acid as a monomer unit, wherein the carboxyl group is introduced by using (meth)acrylic acid as a monomer unit; it may be a copolymer containing (meth)acrylic acid alkyl ester as a monomer unit in addition to (meth)acrylic acid; it may also be a copolymer containing a polymerizable monomer other than (meth)acrylic acid and (meth)acrylic acid alkyl ester (such as a monomer having an ethylenic unsaturated group) as a monomer component in addition to (meth)acrylic acid.

進一步地，含羧基的鹼可溶性聚合物可通過具有羧基的聚合性單體與其它聚合性單體進行自由基聚合而得到，特別是由(甲基)丙烯酸酯、乙烯性不飽和羧酸和其它可共聚單體共聚而成的(甲基)丙烯酸酯系聚合物。 Furthermore, the carboxyl-containing alkali-soluble polymer can be obtained by free radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers, in particular, a (meth)acrylate polymer obtained by copolymerization of (meth)acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers.

所述的(甲基)丙烯酸酯可以是(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸二乙胺基乙酯、(甲基)丙烯酸酯二甲胺基乙酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸糠基酯、(甲基)丙烯酸縮水甘油酯等。這些(甲基)丙烯酸酯可以單獨使用，也可以兩種以上組合使用。 The (meth)acrylate can be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, furfuryl (meth)acrylate, glycidyl (meth)acrylate, etc. These (meth)acrylates can be used alone or in combination of two or more.

所述的乙烯性不飽和羧酸可以是丙烯酸、甲基丙烯酸、丁烯酸、馬來酸、富馬酸、衣康酸，特別佳為丙烯酸、甲基丙烯酸。這些乙烯性不飽和羧酸可以單獨使用，也可以兩種以上組合使用。 The ethylenically unsaturated carboxylic acid can be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and acrylic acid and methacrylic acid are particularly preferred. These ethylenically unsaturated carboxylic acids can be used alone or in combination of two or more.

所述的其它可共聚單體可以是(甲基)丙烯醯胺、(甲基)丙烯酸正丁酯、苯乙烯、乙烯基萘、(甲基)丙烯晴、乙酸乙烯基酯、乙烯基環己烷等。這些其它可共聚單體可以單獨使用，也可以兩種以上組合使用。 The other copolymerizable monomers mentioned above may be (meth)acrylamide, n-butyl (meth)acrylate, styrene, vinylnaphthalene, (meth)acrylonitrile, vinyl acetate, vinylcyclohexane, etc. These other copolymerizable monomers may be used alone or in combination of two or more.

鹼可溶性聚合物可以單獨一種使用，也可以兩種以上組合使用。作為組合兩種以上使用的鹼可溶性聚合物，可列舉出由不同共聚成分構成的兩種以上的鹼可溶性聚合物、不同重均分子量的兩種以上的鹼可溶性聚合物、不同分散度的兩種以上的鹼可溶性聚合物等。 Alkali-soluble polymers can be used alone or in combination of two or more. Examples of alkali-soluble polymers used in combination of two or more include two or more alkali-soluble polymers composed of different copolymer components, two or more alkali-soluble polymers with different weight average molecular weights, and two or more alkali-soluble polymers with different dispersities.

在本發明的感光性樹脂組合物中，對鹼可溶性聚合物的重均分子量沒有特別限制，其應與具體應用環境相適應。從機械強度與鹼顯影性方面綜合考慮，重均分子量較佳為15000-200000，更佳為30000-150000，特別佳為30000-120000。當重均分子量大於15000時，曝光後耐顯影液性有進一步提高的傾向，當該重均分子量小於200000時，顯影時間有變得更短的傾向，且可以保持與光引發劑等其它組分的相容性。鹼可溶性聚合物的重均分子量通過凝膠滲透色譜法(GPC)進行測定，通過使用標準聚苯乙烯的標準曲線進行換算而得到。 In the photosensitive resin composition of the present invention, there is no particular restriction on the weight average molecular weight of the alkali-soluble polymer, which should be adapted to the specific application environment. Considering the mechanical strength and alkali developability, the weight average molecular weight is preferably 15,000-200,000, more preferably 30,000-150,000, and particularly preferably 30,000-120,000. When the weight average molecular weight is greater than 15,000, the developer resistance after exposure tends to be further improved. When the weight average molecular weight is less than 200,000, the developing time tends to be shorter, and the compatibility with other components such as the photoinitiator can be maintained. The weight average molecular weight of the alkali-soluble polymer is measured by gel permeation chromatography (GPC) and converted using a standard curve of standard polystyrene.

進一步地，從鹼顯影性良好的角度考慮，鹼可溶性聚合物的酸值較佳為50-300mgKOH/g，更佳為50-250mgKOH/g，進一步較佳為70-250mgKOH/g，特別佳為100-250mgKOH/g。當鹼可溶性樹脂的酸值低於50mgKOH/g時，難以確保充分的顯影速度，當超過300mgKOH/g時，密合性減小，容易發生圖案短路，且易出現組合物貯存穩定性降低、黏度上升的問題。 Furthermore, from the perspective of good alkali development, the acid value of the alkali-soluble polymer is preferably 50-300 mgKOH/g, more preferably 50-250 mgKOH/g, further preferably 70-250 mgKOH/g, and particularly preferably 100-250 mgKOH/g. When the acid value of the alkali-soluble resin is lower than 50 mgKOH/g, it is difficult to ensure a sufficient development speed. When it exceeds 300 mgKOH/g, the adhesion is reduced, the pattern is prone to short circuit, and the storage stability of the composition is reduced and the viscosity is increased.

鹼可溶性樹脂的分子量分佈[重均分子量(Mw)/數均分子量(Mn)]較佳為1.5-6.0，特別佳為1.8-3.7。當分子量分佈處於所述範圍時，顯影性優異。 The molecular weight distribution of the alkali-soluble resin [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 1.5-6.0, and particularly preferably 1.8-3.7. When the molecular weight distribution is within the above range, the developing property is excellent.

在100質量份感光性樹脂組合物中，鹼可溶性聚合物在組合物中的含量較佳20-70質量份，更佳30-60質量份。當鹼可溶性聚合物的含量在20質量份以上，可確保感光性樹脂組合物對於鍍敷處理、蝕刻處理等的耐久性得到提高，當含量在70質量份以下，有利於提高感光性樹脂組合物的靈敏度。 In 100 parts by mass of the photosensitive resin composition, the content of the alkali-soluble polymer in the composition is preferably 20-70 parts by mass, and more preferably 30-60 parts by mass. When the content of the alkali-soluble polymer is above 20 parts by mass, it can ensure that the durability of the photosensitive resin composition for plating treatment, etching treatment, etc. is improved. When the content is below 70 parts by mass, it is beneficial to improve the sensitivity of the photosensitive resin composition.

具有烯屬不飽和雙鍵的化合物(C) Compounds with olefinic unsaturated double bonds (C)

具有烯屬不飽和雙鍵的化合物可促進感光性樹脂組合物成膜。 Compounds with olefinic unsaturated double bonds can promote the film formation of photosensitive resin compositions.

對具有烯屬不飽和雙鍵的化合物沒有特別限定，只要在分子內具有至少一個乙烯性不飽和鍵的光聚合性化合物就可以使用。示例性地，可列舉出：α,β-不飽和羧酸與多元醇反應而得的化合物、雙酚A類(甲基)丙烯酸酯化合物、α,β-不飽和羧酸與含縮水甘油基的化合物反應而得的化合物、分子內具有氨酯鍵的(甲基)丙烯酸酯化合物等氨基甲酸酯單體、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羥基丙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、β-羥基乙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、β-羥基丙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、苯二甲酸類化合物、(甲基)丙烯酸烷基酯等。這些化合物可以單獨使用，也可兩種以上組合使用。 The compound having an ethylenically unsaturated double bond is not particularly limited, and any photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule may be used. For example, the following can be cited: compounds obtained by reacting α,β-unsaturated carboxylic acid with polyols, bisphenol A (meth)acrylate compounds, compounds obtained by reacting α,β-unsaturated carboxylic acid with glycidyl-containing compounds, carbamate monomers such as (meth)acrylate compounds having carbamate bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, (meth)acrylate alkyl esters, etc. These compounds can be used alone or in combination of two or more.

作為上述α,β-不飽和羧酸與多元醇反應而得的化合物，可例舉出：亞乙基數為2-14的聚乙二醇二(甲基)丙烯酸酯、亞丙基數為2-14的聚丙二醇二(甲基)丙烯酸酯、亞乙基數為2-14且亞丙基數為2-14的聚亞乙基．聚亞丙基二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、EO改性三羥甲基丙烷三(甲基)丙烯酸酯、PO改性三羥甲基丙烷三(甲基)丙烯酸酯、EO,PO改性三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。這些化合物可以單獨使用，也可兩種以上組合使用。在這裡，“EO”表示環氧乙烷，經EO改性的化合物是指具有氧化乙烯基的嵌段結構的化合物。“PO”表示環氧丙烷，經PO改性的化合物是指具有氧化丙烯基的嵌段結構的化合物。 Examples of the compound obtained by reacting the α,β-unsaturated carboxylic acid with a polyol include polyethylene glycol di(meth)acrylate having 2-14 ethylene groups, polypropylene glycol di(meth)acrylate having 2-14 propylene groups, and polyethylene having 2-14 ethylene groups and 2-14 propylene groups. Polypropylene glycol di(meth)acrylate, trihydroxymethylpropane di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, EO-modified trihydroxymethylpropane tri(meth)acrylate, PO-modified trihydroxymethylpropane tri(meth)acrylate, EO,PO-modified trihydroxymethylpropane tri(meth)acrylate, tetrahydroxymethylmethane tri(meth)acrylate, tetrahydroxymethylmethane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, tripropylene glycol di(meth)acrylate, etc. These compounds may be used alone or in combination of two or more. Here, "EO" means ethylene oxide, and the EO-modified compound refers to a compound having a block structure of ethylene oxide groups. "PO" stands for propylene oxide, and a PO-modified compound refers to a compound having a block structure of propylene oxide groups.

作為上述雙酚A類(甲基)丙烯酸酯化合物，可例舉出：2,2-雙{4-[(甲基)丙烯醯氧基多乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基多丙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基多丁氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基多乙氧基多丙氧基]苯基}丙烷等。作為上述2,2-雙{4-[(甲基)丙烯醯氧基多乙氧基]苯基}丙烷，可例舉出：2,2-雙{4-[(甲基)丙烯醯氧基二乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基三乙氧基]苯基}丙烷、2,2-雙{4-[(甲基) 丙烯醯氧基四乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基五乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基六乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基七乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基八乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基九乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十一乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十二乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十三乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十四乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十五乙氧基]苯基}丙烷、2,2-雙{4-[(甲基)丙烯醯氧基十六乙氧基]苯基}丙烷等。上述2,2-雙{4-[(甲基)丙烯醯氧基多乙氧基]苯基}丙烷的1分子內的氧化乙烯基數較佳為4-20，更佳為8-15。這些化合物可以單獨使用，也可兩種以上組合使用。 Examples of the bisphenol A-based (meth)acrylate compound include 2,2-bis{4-[(meth)acryloxypolyethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypolypropoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloxypolybutoxy]phenyl}propane, and 2,2-bis{4-[(meth)acryloxypolyethoxypolypropoxy]phenyl}propane. Examples of the 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane include 2,2-bis{4-[(meth)acryloyloxydiethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytriethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetraethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypentaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyheptaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyoctaethoxy]phenyl}propane, alkane, 2,2-bis{4-[(meth)acryloyloxynonaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydecaethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyundecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxydodecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytridecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxytetradecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxypentadecethoxy]phenyl}propane, 2,2-bis{4-[(meth)acryloyloxyhexadecethoxy]phenyl}propane and the like. The number of oxyethylene groups in one molecule of the above-mentioned 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane is preferably 4-20, more preferably 8-15. These compounds can be used alone or in combination of two or more.

作為上述分子內具有氨酯鍵的(甲基)丙烯酸酯化合物，可例舉出：在β位具有OH基的(甲基)丙烯酸類單體和二異氰酸酯化合物(異佛爾酮二異氰酸酯、2,6-甲苯二異氰酸酯、2,4-甲苯二異氰酸酯、1,6-六亞甲基二異氰酸酯等)的加成反應產物、三[(甲基)丙烯醯氧基四亞乙基二醇異氰酸酯]六亞甲基異氰脲酸酯、EO改性氨酯二(甲基)丙烯酸酯、PO改性氨酯二(甲基)丙烯酸酯、EO,PO改性氨酯二(甲基)丙烯酸酯等。這些化合物可以單獨使用，也可兩種以上組合使用。 Examples of the (meth)acrylate compound having an urethane bond in the above-mentioned molecule include: addition reaction products of a (meth)acrylic monomer having an OH group at the β position and a diisocyanate compound (isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.), tris[(meth)acryloyloxytetraethylene glycol isocyanate] hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO,PO modified urethane di(meth)acrylate, etc. These compounds may be used alone or in combination of two or more.

作為上述壬基苯氧基多乙烯氧基丙烯酸酯，可例舉出：壬基苯氧基四乙烯氧基丙烯酸酯、壬基苯氧基五乙烯氧基丙烯酸酯、壬基苯氧基六乙烯氧基丙烯酸酯、壬基苯氧基七乙烯氧基丙烯酸酯、壬基苯氧基八乙烯氧基丙烯酸酯、壬基苯氧基九乙烯氧基丙烯酸酯、壬基苯氧基十乙烯氧基丙烯酸酯、壬基苯氧基十一乙烯氧基丙烯酸酯等。這些化合物可以單獨使用，也可兩種以上組合使用。 Examples of the nonylphenoxy polyvinyloxy acrylate include nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexavinyloxy acrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxy decavinyloxy acrylate, and nonylphenoxy undecvinyloxy acrylate. These compounds may be used alone or in combination of two or more.

作為上述苯二甲酸類化合物，可例舉出：γ-氯-β-羥基丙基-β’-(甲基)丙烯醯氧基乙基鄰苯二甲酸酯、β-羥基烷基-β’-(甲基)丙烯醯氧基烷基鄰苯二甲酸酯等。這些化合物可以單獨使用，也可兩種以上組合使用。 Examples of the above-mentioned phthalic acid compounds include: γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl phthalate, β-hydroxyalkyl-β'-(meth)acryloyloxyalkyl phthalate, etc. These compounds can be used alone or in combination of two or more.

作為上述(甲基)丙烯酸烷基酯，可例舉出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸羥甲酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸四氫糠基酯、(甲基)丙烯酸異辛酯、乙氧基化壬基酚(甲基)丙烯酸酯、丙二醇聚丙烯醚二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙氧基化聚四氫呋喃二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯等。其中，較佳為(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯。這些化合物可以單獨使用，也可兩種以上組合使用。 Examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and tert-butyl (meth)acrylate. 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)acrylate, ethoxylated nonylphenol (meth)acrylate, propylene glycol polypropylene ether di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, ethoxylated polytetrahydrofurandiol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, etc. Among them, methyl (meth)acrylate, ethyl (meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, ethoxylated trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexaacrylate are preferred. These compounds can be used alone or in combination of two or more.

從提高分辨率、耐鍍覆性、密合性的角度來看，所述具有烯屬不飽和雙鍵的化合物較佳雙酚A類(甲基)丙烯酸酯化合物和分子內具有氨酯鍵的(甲基)丙烯酸酯化合物。從可以提高靈敏度和解析度的角度來看，較佳雙酚A類(甲基)丙烯酸酯化合物。作為雙酚A類(甲基)丙烯酸酯化合物的市售品，示例性地，有2,2-雙{4-[(甲基)丙烯醯氧基多乙氧基]苯基}丙烷(新中村化學工業株式會社制，BPE-200)、2,2-雙{4-[(甲基)丙烯醯氧基多丙氧基]苯基)丙烷(新中村化學工業株式會社制，BPE-5000；日立化成株式會社制，FA-321M)、2,2-雙{4-[(甲基)丙烯醯氧基多丁氧基]苯基}丙烷(新中村化學工業株式會社，BPE-1300)等。 From the perspective of improving resolution, coating resistance, and adhesion, the compound having an ethylenically unsaturated double bond is preferably a bisphenol A (meth)acrylate compound and a (meth)acrylate compound having an urethane bond in the molecule. From the perspective of improving sensitivity and resolution, a bisphenol A (meth)acrylate compound is preferred. As commercially available products of bisphenol A-based (meth)acrylate compounds, there are, for example, 2,2-bis{4-[(meth)acryloyloxypolyethoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-200), 2,2-bis{4-[(meth)acryloyloxypolypropoxy]phenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-5000; manufactured by Hitachi Chemical Co., Ltd., FA-321M), 2,2-bis{4-[(meth)acryloyloxypolybutoxy]phenyl}propane (manufactured by Shin-Nakamura Chemical Co., Ltd., BPE-1300), etc.

在100質量份感光性樹脂組合物中，具有烯屬不飽和雙鍵的化合物(C)的含量較佳20-50質量份，更佳25-45質量份。當所述具有烯屬不飽和雙鍵的化合物的含量在20質量份以上時，感光性樹脂組合物的靈敏度和解析度會進一步提高；當其含量在50質量份以下，感光性樹脂組合物更易薄膜化，且對於蝕刻處理的耐久性進一步提高。 In 100 parts by mass of the photosensitive resin composition, the content of the compound (C) having an olefinic unsaturated double bond is preferably 20-50 parts by mass, more preferably 25-45 parts by mass. When the content of the compound having an olefinic unsaturated double bond is above 20 parts by mass, the sensitivity and resolution of the photosensitive resin composition will be further improved; when its content is below 50 parts by mass, the photosensitive resin composition is easier to form into a thin film, and the durability to etching treatment is further improved.

供氫體(D) Hydrogen donor (D)

本發明的感光性樹脂組合物還包括供氫體，以便改善感光度。雙咪唑類化合物經光照後裂解，產生的單咪唑自由基體積較大，位阻效應使得活性較小，很難單獨引發單體聚合，而如果和供氫體配合使用，則單咪唑自由基容易奪取供氫體上的活潑氫，產生新的活性自由基，進而引發單體聚合。 The photosensitive resin composition of the present invention also includes a hydrogen donor to improve the photosensitivity. After being irradiated with light, the biimidazole compound is cleaved to produce a monoimidazole free radical with a large volume. The steric hindrance effect makes the activity small, and it is difficult to initiate monomer polymerization alone. However, if used in combination with a hydrogen donor, the monoimidazole free radical can easily take the active hydrogen on the hydrogen donor to generate new active free radicals, thereby initiating monomer polymerization.

只要是具有上述特性的供氫體，在具體種類方面就沒有特別限制，可以包括(但不限於)：胺類化合物、羧酸類化合物、含有巰基的有機硫化合物或醇類化合物等。這些化合物可單獨使用，或以其中的兩種以上組合使用。 As long as the hydrogen donor has the above characteristics, there is no special restriction on the specific type, which may include (but not limited to): amine compounds, carboxylic acid compounds, organic sulfur compounds containing hydroxyl groups or alcohol compounds, etc. These compounds can be used alone or in combination of two or more thereof.

胺類化合物沒有特別限制，可以包括(但不限於)：脂肪族胺化合物，如三乙醇胺、甲基二乙醇胺、三異丙醇胺等；芳香族胺化合物，如4-二甲氨基苯甲酸甲酯、4-二甲氨基苯甲酸乙酯、4-二甲氨基苯甲酸異戊酯、4-二甲氨基苯甲酸2-乙基己酯、2-二甲氨基乙基苯甲酸酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲氨基)二苯甲酮、4,4’-雙(二乙氨基)二苯甲酮等。 There is no special restriction on amine compounds, and they may include (but are not limited to): aliphatic amine compounds, such as triethanolamine, methyldiethanolamine, triisopropanolamine, etc.; aromatic amine compounds, such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

羧酸類化合物沒有特別限制，可以包括(但不限於)：芳香族雜乙酸、苯基硫代乙酸、甲基苯基硫代乙酸、乙基苯基硫代乙酸、甲基乙基苯基硫代乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、二甲氧基苯基硫代乙酸、氯苯基硫代乙酸、二氯苯基硫代乙酸、N-苯基甘氨酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘氨酸、萘氧基乙酸等。 There is no particular limitation on carboxylic acid compounds, and they may include (but are not limited to): aromatic heteroacetic acid, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

含有巰基的有機硫化合物沒有特別限制，可以包括(但不限於)：2-巰基苯並噻唑(MBO)、2-巰基苯並咪唑(MBI)、十二烷基硫醇、乙二醇雙(3-巰基丁酸酯)、1,2-丙二醇雙(3-巰基丁酸酯)、二乙二醇雙(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、辛二醇雙(3-巰基丁酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)、季戊四醇四(3-巰基丁酸酯)、二季戊四醇六(3-巰基丁酸酯)、乙二醇雙(2-巰基丙酸酯)、丙二醇雙(2-巰基丙酸酯)、二乙二醇雙(2-巰基丙酸酯)、丁二醇雙(2-巰基丙酸酯)、辛二醇雙(2-巰基丙酸酯)、三羥甲基丙烷三(2-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)、二季戊四醇六(2-巰基丙酸酯)、乙二醇雙(3-巰基異丁酸酯)、1,2-丙二醇雙(3-巰基異丁酸酯)、二乙二醇雙(3-巰基異丁酸酯)、丁二醇雙(3-巰基異丁酸酯)、辛二醇雙(3-巰基異丁酸酯)、三羥甲基丙烷三(3-巰基異丁酸酯)、季戊四醇四(3-巰基異丁酸酯)、二季戊四醇六(3-巰基異丁酸酯)、乙二醇雙(2-巰基異丁酸酯)、1,2-丙二醇雙(2-巰基異丁酸酯)、二乙二醇雙(2-巰基異丁酸酯)、丁二醇雙(2-巰基異丁酸酯)、辛二醇雙(2-巰基異丁酸酯)、三羥甲基丙烷三(2-巰基異丁酸酯)、季戊四醇四(2-巰基異丁酸酯)、二季戊四醇六(2-巰基異丁酸酯)、乙二醇雙(4-巰基戊酸酯)、1,2-丙二醇雙(4-巰基異戊酸酯)、二乙二醇雙(4-巰基戊酸酯)、丁二醇雙(4-巰基戊酸酯)、辛二醇雙(4-巰基戊酸酯)、三羥甲基丙烷三(4-巰基戊酸酯)、季戊四醇四(4-巰基戊酸酯)、二季戊四醇六(4-巰基戊酸酯)、乙二醇雙(3-巰基戊酸酯)、1,2-丙二醇雙(3-巰基戊酸酯)、二乙二醇雙(3-巰基戊酸酯)、丁二醇雙(3-巰基戊酸酯)、辛二醇雙(3-巰基戊酸酯)、三羥甲基丙烷三(3-巰基戊酸酯)、季戊四醇四(3-巰基戊酸酯)、二季戊四醇六(3-巰基戊酸酯)等脂肪族二級多官能硫醇化合物；芳香族二級多官能硫醇化合物，如鄰苯二甲酸二(1-巰基乙酯)、鄰苯二甲酸二(2-巰基丙酯)、鄰苯二甲酸二(3-巰基丁酯)、鄰苯二甲酸二(3-巰基異丁酯)等。 There is no particular limitation on the organic sulfur compound containing alkyl groups, and the organic sulfur compound may include (but is not limited to): 2-alkylbenzothiazole (MBO), 2-alkylbenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-alkylbutyrate), 1,2-propylene glycol bis(3-alkylbutyrate), diethylene glycol bis(3-alkylbutyrate), butanediol bis(3-alkylbutyrate), octanediol bis(3-alkylbutyrate), trihydroxymethylpropane tris(3-alkylbutyrate), pentaerythritol tetra(3-alkylbutyrate), dipentaerythritol hexa(3-alkylbutyrate), ethylene glycol bis(2-alkylpropionate), propylene glycol bis(2-alkylpropionate), diethylene glycol bis(2-alkylpropionate), Ester), butanediol di(2-butyl propionate), octanediol di(2-butyl propionate), trihydroxymethylpropane tri(2-butyl propionate), pentaerythritol tetra(3-butyl propionate), dipentaerythritol hexa(2-butyl propionate), ethylene glycol di(3-butyl isobutyrate), 1,2-propylene glycol di(3-butyl isobutyrate), Diethylene glycol di(3-butylene isobutyrate), butanediol di(3-butylene isobutyrate), octanediol di(3-butylene isobutyrate), trihydroxymethylpropane tri(3-butylene isobutyrate), pentaerythritol tetra(3-butylene isobutyrate), dipentaerythritol hexa(3-butylene isobutyrate), ethylene glycol di(2-butylene isobutyrate), 1, 2-Propanediol di(2-butyl isobutyrate), diethylene glycol di(2-butyl isobutyrate), butanediol di(2-butyl isobutyrate), octanediol di(2-butyl isobutyrate), trihydroxymethylpropane tri(2-butyl isobutyrate), pentaerythritol tetra(2-butyl isobutyrate), dipentaerythritol hexa(2-butyl isobutyrate) , ethylene glycol di(4-benzene valerate), 1,2-propylene glycol di(4-benzene isovalerate), diethylene glycol di(4-benzene valerate), butanediol di(4-benzene valerate), octanediol di(4-benzene valerate), trihydroxymethylpropane tri(4-benzene valerate), pentaerythritol tetra(4-benzene valerate), dipentaerythritol tetra(4-benzene valerate) Aliphatic secondary multifunctional thiol compounds such as ethylene glycol hexa(4-butyl valerate), ethylene glycol di(3-butyl valerate), 1,2-propylene glycol di(3-butyl valerate), diethylene glycol di(3-butyl valerate), butanediol di(3-butyl valerate), octanediol di(3-butyl valerate), trihydroxymethylpropane tri(3-butyl valerate), pentaerythritol tetra(3-butyl valerate), dipentaerythritol hexa(3-butyl valerate); aromatic secondary multifunctional thiol compounds such as di(1-butyl ethyl ester), di(2-butyl propyl ester), di(3-butyl butyl ester), di(3-butyl isobutyl ester), etc.

醇類化合物沒有特別限制，可以包括(但不限於)：甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、新戊醇、正己醇、環已醇、乙二醇、1,2-丙二醇、1,2,3-丙三醇、苯甲醇、苯乙醇等。 There is no special restriction on alcohol compounds, and they may include (but are not limited to): methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, 1,2-propylene glycol, 1,2,3-propylene triol, benzyl alcohol, phenylethyl alcohol, etc.

在100質量份感光性樹脂組合物中，供氫體(D)的含量可以為0.01-20重量份，較佳0.01-10重量份。當供氫體的含量在上述範圍內，對調控感光性樹脂組合物的感光度是有利的。 In 100 parts by weight of the photosensitive resin composition, the content of the hydrogen donor (D) can be 0.01-20 parts by weight, preferably 0.01-10 parts by weight. When the content of the hydrogen donor is within the above range, it is beneficial to adjust the sensitivity of the photosensitive resin composition.

其它任選的助劑(E) Other optional additives (E)

除了上述各組分，任選地，本發明的感光性樹脂組合物中還可以根據需要包含適量的其它助劑。示例性地，助劑可以包括其它光引發劑和/或增感劑、有機溶劑、染料、顏料、光顯色劑、填充劑、增塑劑、穩定劑、塗布助劑、剝離促進劑等中的至少一種。 In addition to the above components, the photosensitive resin composition of the present invention may optionally contain an appropriate amount of other additives as needed. For example, the additives may include at least one of other photoinitiators and/or sensitizers, organic solvents, dyes, pigments, photochromic agents, fillers, plasticizers, stabilizers, coating aids, and stripping accelerators.

所述其它光引發劑和/或增感劑可包括(但不限於)：雙咪唑類、芳香族酮類、蒽醌類、苯偶姻和苯偶姻烷基醚類、肟酯類、三嗪類、香豆素類、噻噸酮類、吖啶類及其它本領域技術人員已知的光引發劑。 The other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, oxime esters, triazines, coumarins, thioxanthines, acridines and other photoinitiators known to those skilled in the art.

示例性地，雙咪唑類化合物包括：2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’,5-三(鄰氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-二咪唑、2,2’,5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-氟苯基)-4-(鄰氯苯基)-5-(3,4-二甲氧基苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2-氟苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-甲氧基苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-氯-5-硝基苯基)-4,4’-二(3,4-二甲氧基苯基)-5,5’-二(鄰氯苯基)-二咪唑、2,2’-二(2-氯-5-硝基苯基)-4-(3,4-二甲氧基苯基)-5-(鄰氯苯基)-4’,5’-二苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’-二(3,4-二甲氧基苯基)-5,5’-二(鄰氯苯基)-二咪唑、2-(2,4-二氯苯基)-4-(3,4-二甲氧基苯基)-2’,5-二(鄰氯苯基)-4’,5’-二苯基-二咪唑、2-(2,4-二氯苯基)-2’-(鄰氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑及其相似物。這些雙咪唑類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, the biimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole, 2,2',5-tri(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole, 2,2',5-tri(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-biimidazole, 2,2'-bis(2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-diimidazole, -bis(2-chloro-5-nitrophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5'-bis(o-chlorophenyl)-diimidazole, 2,2'-bis(2-chloro-5-nitrophenyl)-4-(3,4-dimethoxyphenyl)-5-(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-5,5' -bis(o-chlorophenyl)-diimidazole, 2-(2,4-dichlorophenyl)-4-(3,4-dimethoxyphenyl)-2',5-bis(o-chlorophenyl)-4',5'-diphenyl-diimidazole, 2-(2,4-dichlorophenyl)-2'-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole and their analogs. These bisimidazole compounds can be used alone or in combination of two or more.

示例性地，芳香族酮類化合物包括：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、二苯甲酮、4-苯甲醯基二苯硫醚、4-苯甲醯基-4’-甲基二苯硫醚、4-苯甲醯基-4’-乙基二苯硫醚、4-苯甲醯基-4’-丙基二苯硫醚、4,4’-雙(二乙基氨基)二苯甲酮、4-對甲苯巰基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮、4,4’-雙(二甲氨基)二苯甲酮、4,4’-雙(甲基、乙基氨基)二苯甲酮、苯乙酮二甲基縮酮、苯偶醯二甲基縮酮、α,α’-二甲基苯偶醯縮酮、α,α’-二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙酮、1-羥基環己基苯甲酮、2-羥基-2-甲基-1-對羥乙基醚基苯基丙酮、2-甲基1-(4-甲巰基苯基)-2-嗎啉1-丙酮、2-苄基-2-二甲氨基-1-(4-嗎啉苯基)1-丁酮、苯基雙(2,4,6-三甲基苯甲醯基)氧膦、2,4,6(三甲基苯甲醯基)二苯基氧化膦、2-羥基-1-{3-[4-(2-羥基-2-甲基-丙醯基)-苯基]-1,1,3-三甲基-茚-5-基}-2-甲基丙酮、2-羥基-1-{1-[4-(2-羥基-2-甲基-丙醯基)-苯基]-1,3,3-三甲基-茚-5-基}-2-甲基丙酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、4-(2-羥基乙氧基)-苯基-(2-羥基-2-丙基)酮及其相似物。這些芳香族酮類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino) diphenyl Benzophenone, 4-p-tolylbenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethylamino)benzophenone, acetophenone dimethyl ketal, benzoyl dimethyl ketal, α,α'-dimethylbenzoyl ketal, α,α'-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone , 2-Hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, 2-methyl 1-(4-methylphenyl)-2-pyroline 1-acetone, 2-benzyl-2-dimethylamino-1-(4-pyrolinephenyl) 1-butanone, phenylbis(2,4,6-trimethylbenzyl)phosphine oxide, 2,4,6(trimethylbenzyl)diphenylphosphine oxide, 2-Hydroxy-1-{3-[4-(2-hydroxy-2-methyl-propionyl )-phenyl]-1,1,3-trimethyl-inden-5-yl}-2-methylpropanone, 2-hydroxy-1-{1-[4-(2-hydroxy-2-methyl-propionyl)-phenyl]-1,3,3-trimethyl-inden-5-yl}-2-methylpropanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl-(2-hydroxy-2-propyl)ketone and the like. These aromatic ketone compounds can be used alone or in combination of two or more.

示例性地，蒽醌類化合物包括：2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、2,3-二甲基蒽醌、2-乙基蒽-9,10-二乙酯、1,2,3-三甲基蒽-9,10-二辛脂、2-乙基蒽-9,10-二(4-氯丁酸甲酯)、2-{3-[(3-乙基氧雜環丁烷-3-基)甲氧基]-3-氧代丙基}蒽-9,10-二乙酯、9,10-二丁氧基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二(3-氯丙氧基)蒽、9,10-二(2-羥基乙巰基)蒽、9,10-二(3-羥基-1-丙巰基)蒽及其相似物。這些蒽醌類化合物可以單獨使用或兩種以上組合使用。 Illustratively, anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl ester, 1,2,3-trimethylanthracene-9,10-dioctyl ester, 2-ethylanthracene-9,10-di(4-chlorobutyric acid methyl ester), 2-{3-[(3-ethyloxycyclobutane-3-yl)methoxy]-3-oxopropyl}anthracene-9,10-diethyl ester, 9,10-dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-di(3-chloropropoxy)anthracene, 9,10-di(2-hydroxyethinyl)anthracene, 9,10-di(3-hydroxy-1-propinyl)anthracene, and the like. These anthraquinone compounds can be used alone or in combination of two or more.

示例性地，苯偶姻和苯偶姻烷基醚類化合物包括：苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚及其相似物。這些苯偶姻和苯偶姻烷基醚類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like. These benzoin and benzoin alkyl ether compounds can be used alone or in combination of two or more.

示例性地，肟酯類化合物可以包括：1-(4-苯硫基苯基)-正辛烷-1,2-二酮-2-苯甲酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-乙烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-丁烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-丙烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-1-環己基-甲烷-1-酮-乙酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-(3-環戊基)-丙烷-1-酮-乙酸肟酯、1-(4-苯硫基苯基)-(3-環戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯硫基苯基)-(3-環己基)-丙烷-1,2-二酮-2-環己基甲酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-(3-環戊基)-丙烷-1,2-二酮-2-乙酸肟酯、 1-(6-鄰甲基苯甲醯基-9-乙基咔唑-3-基)-(3-環戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯甲醯基二苯硫醚)-(3-環戊基丙酮)-1-肟乙酸酯、1-(6-鄰甲基苯甲醯基-9-乙基咔唑-3-基)-(3-環戊基丙酮)-1-肟環己基甲酸酯、1-(4-苯甲醯基二苯硫醚)-3-環戊基丙酮)-1-肟環己基甲酸酯、1-(6-鄰甲基苯甲醯基-9-乙基咔唑-3-基)-(3-環戊基)-丙烷-1,2-二酮-2-鄰甲基苯甲酸肟酯、1-(4-苯硫基苯基)-(3-環戊基)-丙烷-1,2-二酮-2-環己基甲酸肟酯、1-(4-噻吩甲醯基-二苯硫醚-4’-基)-3-環戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯甲醯基二苯硫醚)-(3-環戊基)-丙烷-1,2-二酮-2-肟乙酸酯、1-(6-硝基-9-乙基咔唑-3-基)-3-環己基-丙烷-1-酮-乙酸肟酯、1-(6-鄰甲基苯甲醯基-9-乙基咔唑-3-基)-3-環己基-丙烷-1-酮-乙酸肟酯、1-(6-噻吩甲醯基-9-乙基咔唑-3-基)-(3-環己基丙酮)-1-肟乙酸酯、1-(6-呋喃糠甲醯基-9-乙基咔唑-3-基)-(3-環戊基丙酮)-1-肟乙酸酯、1,4-二苯基丙烷-1,3-二酮-2-乙酸肟酯、1-(6-糠醯基-9-乙基咔唑-3-基)-(3-環己基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(4-苯硫基苯基)-(3-環已基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(6-呋喃糠甲醯基-9-乙基咔唑-3-基)-(3-環己基丙酮)-1-肟乙酸酯、1-(4-苯硫基苯基)-(3-環已基)-丙烷-1,2-二酮-3-苯甲酸肟酯、1-(6-噻吩甲醯基-9-乙基咔唑-3-基)-(3-環己基)-丙烷-1,2-二酮-2-乙酸肟酯、2-[(苯甲醯氧基)亞氨基]-1-苯基丙烷-1-酮、1-苯基-1,2-丙二酮-2-(氧代乙醯基)肟、1-(4-苯硫基苯基)-2-(2-甲基苯基)-乙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-7-硝基芴-2-基)-3-環己基-丙烷-1-酮-乙酸肟酯、1-{4-[4-(噻吩-2-甲醯基)苯硫基]苯基}-3-環戊基丙烷-1,2-二酮-2-乙酸肟酯、1-[9,9-二丁基-2-基]-3-環己基丙基丙烷-1,2-二酮-2-乙酸肟酯、1-[6-(2-苯甲醯氧基亞氨基)-3-環己基丙基-9-乙基咔唑-3-基]辛烷-1,2-二酮-2-苯甲酸肟酯、1-(7-硝基-9,9-二烯丙基芴-2-基)-1-(2-甲基苯基)甲酮-乙酸肟酯、1-[6-(2-甲基苯甲醯基)-9-乙基咔唑-3-基]-3-環戊基-丙烷-1-酮-苯甲酸肟酯、 1-[7-(2-甲基苯甲醯基)-9,9-二丁基芴-2-基]-3-環己基丙烷-1,2-二酮-2-乙酸肟酯、1-[6-(呋喃-2-甲醯基)-9-乙基咔唑-3-基]-3-環己基丙烷-1,2-二酮-2-乙氧甲醯肟酯及其相似物。這些肟酯類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, the oxime ester compound may include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-ethane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-butane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-propane-1-one-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-1-cyclohexane 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1-one-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-benzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-(3-cyclopentyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(6- 1-(4-Benzyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime acetate, 1-(6-(2-methylbenzyl)-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(4-Benzyldiphenylsulfide)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 1-(6-(2-methylbenzyl)-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime cyclohexylcarboxylate, 2-o-Methylbenzoic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclopentyl)-propane-1,2-dione-2-cyclohexylcarboxylic acid oxime ester, 1-(4-thienyl-diphenyl sulfide-4'-yl)-3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1-(4-benzoyl diphenyl sulfide)-(3-cyclopentyl)-propane-1,2-dione-2-oxime acetate, 1-(6-nitro-9-ethylcarbazole-3-yl)-3-cyclohexyl-propane-1-one-acetic acid oxime ester, 1-(6-o-methylbenzoyl-9-ethylcarbazole-3-yl)-3-cyclohexyl- Propane-1-one-acetic acid oxime ester, 1-(6-thienyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate, 1-(6-furanofuryl-9-ethylcarbazole-3-yl)-(3-cyclopentylacetone)-1-oxime acetate, 1,4-diphenylpropane-1,3-dione-2-acetic acid oxime ester, 1-(6-furfuryl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester, 1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester 、1-(6-furanofurylcarbonyl-9-ethylcarbazole-3-yl)-(3-cyclohexylacetone)-1-oxime acetate、1-(4-phenylthiophenyl)-(3-cyclohexyl)-propane-1,2-dione-3-benzoic acid oxime ester、1-(6-thienylcarbonyl-9-ethylcarbazole-3-yl)-(3-cyclohexyl)-propane-1,2-dione-2-acetic acid oxime ester、2-[(benzoyloxy)imino]-1-phenylpropane-1-one、1-phenyl-1,2-propanedione-2-(oxoacetyl)oxime、1-(4-phenylthiophenyl)-2-(2-methylphenyl) -ethane-1,2-dione-2-acetic acid oxime, 1-(9,9-dibutyl-7-nitrofluoren-2-yl)-3-cyclohexyl-propane-1-one-acetic acid oxime, 1-{4-[4-(thiophene-2-carbonyl)phenylthio]phenyl}-3-cyclopentylpropane-1,2-dione-2-acetic acid oxime, 1-[9,9-dibutyl-2-yl]-3-cyclohexylpropylpropane-1,2-dione-2-acetic acid oxime, 1-[6-(2-benzoyloxyimino)-3-cyclohexylpropyl-9-ethylcarbazol-3-yl]octane-1,2-dione-2-benzoic acid oxime Ester, 1-(7-nitro-9,9-diallylfluoren-2-yl)-1-(2-methylphenyl)methanone-acetic acid oxime ester, 1-[6-(2-methylbenzoyl)-9-ethylcarbazole-3-yl]-3-cyclopentyl-propane-1-one-benzoic acid oxime ester, 1-[7-(2-methylbenzoyl)-9,9-dibutylfluoren-2-yl]-3-cyclohexylpropane-1,2-dione-2-acetic acid oxime ester, 1-[6-(furan-2-carbonyl)-9-ethylcarbazole-3-yl]-3-cyclohexylpropane-1,2-dione-2-ethoxycarbonyl oxime ester and the like. These oxime ester compounds can be used alone or in combination of two or more.

示例性地，三嗪類化合物包括：2-(4-乙基聯苯)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4-亞甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、1,1,1,3,3,3-六氟異丙基-3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸酯、乙基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、2-乙氧基乙基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、環己基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、芐基-2-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、3-{氯-4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、3-{4-[2,4-雙(三氯甲基)-s-三嗪-6-基]苯硫基}丙醯胺、2,4-雙(三氯甲基)-6-p-甲氧基苯乙烯基-s-三嗪、2,4-雙(三氯甲基)-6-(1-p-二甲基胺基苯基)-1,3-丁二烯基-s-三嗪、2-三氯甲基-4-胺基-6-p-甲氧基苯乙烯基-s-三嗪及其相似物。這些三嗪類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, the triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methyleneoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}propanoate, ethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, 2-ethoxyethyl-2-{4-[2,4-bis(trichloromethyl)-s-triazine-6-yl]phenylthio}acetate, Hexyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate, benzyl-2-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio} acetate, 3-{chloro-4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionic acid, 3-{4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio}propionamide, 2,4-bis(trichloromethyl)-6-p-methoxyphenylvinyl-s-triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl)-1,3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxyphenylvinyl-s-triazine and the like. These triazine compounds can be used alone or in combination of two or more.

示例性地，香豆素類化合物包括：3,3’-羰基雙(7-二乙胺香豆素)、3-苯甲醯基-7-二乙胺香豆素、3,3’-羰基雙(7-甲氧基香豆素)、7-二乙氨基-4-甲基香豆素、3-(2-苯並噻唑)-7-(二乙基胺基)香豆素、7-(二乙氨基)-4-甲基-2H-1-苯並吡喃-2-酮[7-(二乙氨基)-4-甲基香豆素]、3-苯甲醯基-7-甲氧基香豆素及其相似物。這些香豆素類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, coumarin compounds include: 3,3'-carbonylbis(7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3,3'-carbonylbis(7-methoxycoumarin), 7-diethylamino-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one [7-(diethylamino)-4-methylcoumarin], 3-benzoyl-7-methoxycoumarin and the like. These coumarin compounds can be used alone or in combination of two or more.

示例性地，噻噸酮類化合物包括：噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、2-氯噻噸酮、1-氯-4-丙氧基噻噸酮、異丙基噻噸酮、二異丙基噻噸酮及相似物。這些噻噸酮類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, the thiothione compounds include: thiothione, 2,4-dimethylthiothione, 2,4-diethylthiothione, 2,4-diisopropylthiothione, 2-chlorothiothione, 1-chloro-4-propoxythiothione, isopropylthiothione, diisopropylthiothione and the like. These thiothione compounds can be used alone or in combination of two or more.

示例性地，吖啶類化合物包括：9-苯基吖啶、9-對甲基苯基吖啶、9-間甲基苯基吖啶、9-鄰氯苯基吖啶、9-鄰氟苯基吖啶、1,7-二(9-吖啶基)庚烷、9-乙基吖啶、9-(4-溴苯基)吖啶、9-(3-氯苯基)吖啶、1,7-雙(9-吖啶)庚烷、1,5-雙(9-吖啶戊烷)、1,3-雙(9-吖啶)丙烷及其相似物。這些吖啶類化合物可以單獨使用或兩種以上組合使用。 Exemplarily, acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, 1,7-di(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3-chlorophenyl)acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinylpentane), 1,3-bis(9-acridinyl)propane and the like. These acridine compounds can be used alone or in combination of two or more.

有機溶劑只要能夠溶解前述各組分即可，示例性地，可以是二醇醚系溶劑、醇系溶劑、酯系溶劑、酮系溶劑、醯胺系溶劑、含氯溶劑等，較佳特別考慮著色劑、鹼可溶性聚合物的溶解性、塗布性、安全性等因素來進行選擇。較佳地，有機溶劑可以是乙基溶纖劑(乙二醇單乙基醚)、甲基溶纖劑(乙二醇單甲基醚)、丁基溶纖劑(乙二醇單丁基醚)、甲基甲氧基丁醇(3-甲基-3-甲氧基丁醇)、丁基卡必醇(二甘醇單丁基醚)、乙二醇單乙基醚乙酸酯、乙二醇單叔丁基醚、丙二醇單甲基醚乙酸酯、丙二醇單甲基醚(1-甲氧基-2-丙醇)、丙二醇單乙基醚(1-乙氧基-2-丙醇)、丙二醇單乙基醚乙酸酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、乙酸溶纖劑(乙二醇單甲基醚乙酸酯)、乙酸甲氧基丁酯(乙酸3-甲氧基丁酯)、乙酸3-甲基-3-甲氧基丁酯、3-乙氧基丙酸乙酯(EEP)、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、2-丁酮(MEK)、甲基異丁基酮(MIBK)、環己酮、環戊酮、二丙酮醇(4-羥基-4-甲基-2-戊酮)、異佛爾酮(3,5,5-三甲基-2-環己烯-1-酮)、二異丁基酮(2,6-二甲基-4-庚酮)、N-甲基吡咯烷酮(4-甲基氨基內醯胺或NMP)、甲醇、乙醇、異丙醇、正丙醇、異丁醇、正丁醇等。這些溶劑可單獨使用，或以其中兩種以上組合使用。 The organic solvent can be any solvent as long as it can dissolve the aforementioned components. For example, it can be a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, a chlorine-containing solvent, etc. It is preferably selected by taking into account the solubility, coating properties, safety, etc. of the colorant and alkali-soluble polymer. Preferably, the organic solvent can be ethyl solvent (ethylene glycol monoethyl ether), methyl solvent (ethylene glycol monomethyl ether), butyl solvent (ethylene glycol monobutyl ether), methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, acetic acid solvent (ethylene glycol monomethyl ether acetate), acetic acid Methoxybutyl ester (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-cyclohexene-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactamide or NMP), methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, etc. These solvents can be used alone or in combination of two or more thereof.

示例性地，染料、顏料及光顯色劑包括：三(4-二甲基氨基苯基)甲烷、三(4-二甲基氨基-2甲基苯基)甲烷、熒烷染料、甲苯磺酸一水合物、鹼性品紅、酞菁綠及酞菁藍等酞菁系、金胺鹼、副品紅、結晶紫、甲基橙、尼羅藍2B、維多利亞藍、孔雀綠、金剛綠、鹼性藍20、豔綠、伊紅、乙基紫、赤蘚紅鈉鹽B、甲基綠、苯酚酞、茜素紅S、百里香酚酞、甲基紫2B、喹那定紅、玫瑰紅鈉瓊脂、米塔尼爾黃、百里香酚磺酞、二甲苯酚藍、甲基橘、橘IV、二苯基流卡巴腙、2,7-二氯熒光素、泛甲基紅、剛果紅、本佐紅紫4B、α-萘基紅、非那西汀、甲基紫、維多利亞純藍BOH、羅丹明6G、二苯基胺、二苄基苯胺、三苯基胺、二乙基苯胺、二-對伸二胺、對甲苯胺、苯並三氮唑、甲基苯丙***、4,4’-聯二胺、鄰氯苯胺、白色結晶紫、白色孔雀綠、白色苯胺、白色甲基紫、偶氮系等有機顏料，二氧化鈦等無機顏料。在具有良好對比度的考量下，較佳使用三(4-二甲基氨基苯基)甲烷(即隱色結晶紫，LCV)。這些染料、顏料及光顯色劑可以單獨一種使用，也可兩種以上混合使用。 For example, dyes, pigments and photochromic agents include: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, alkane dyes, toluenesulfonic acid monohydrate, alkali fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanine series, auramine, para-fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, adamantium green, alkali blue 20, brilliant green, eosin, ethyl violet, erythromycin sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadin red, rose red sodium agar, Mittanil yellow, thyme ... Phenolsulfonphthalein, xylenol blue, methyl orange, orange IV, diphenylcarbazone, 2,7-dichlorofluorescein, panmethyl red, Congo red, Benzyl red 4B, α-naphthyl red, phenacetin, methyl violet, Victoria blue BOH, rhodamine 6G, diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-aminodiamine, p-toluidine, benzotriazole, methyl benzotriazole, 4,4'-diamine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, azo series and other organic pigments, and titanium dioxide and other inorganic pigments. In consideration of good contrast, tris (4-dimethylaminophenyl) methane (i.e., hidden crystal violet, LCV) is preferably used. These dyes, pigments and photochromic agents can be used alone or in combination of two or more.

示例性地，填充劑包括：二氧化矽、氧化鋁、滑石、碳酸鈣、硫酸鋇等填充劑(不包含上述無機顏料)。填充劑可以單獨一種使用，也可兩種以上混合使用。 For example, fillers include: silicon dioxide, aluminum oxide, talc, calcium carbonate, barium sulfate and other fillers (excluding the above-mentioned inorganic pigments). Fillers can be used alone or in combination of two or more.

示例性地，增塑劑包括：鄰苯二甲酸二丁酯、鄰苯二甲酸二庚酯、鄰苯二甲酸二辛酯、鄰苯二甲酸二烯丙酯等鄰苯二甲酸酯，三甘醇二乙酸酯、四乙二醇二乙酸酯等乙二醇酯，對甲苯磺醯胺、苯磺醯胺、正丁基苯磺醯胺等磺醯胺類，磷酸三苯酯、三甲基磷酸酯、三乙基磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、三二甲苯基磷酸酯、甲苯基二苯基磷酸酯、三二甲苯基磷酸酯、2-萘基二苯基磷酸酯、甲苯基二2,6-二甲苯基磷酸酯、芳香族縮合磷酸酯、三(氯丙基)磷酸酯、三(三溴新戊基)磷酸酯、含鹵縮合磷酸酯，二辛酸三甘醇酯，二(2-乙基己酸)三甘醇酯、二庚酸四甘醇酯、癸二酸二乙酯、辛二酸二丁酯、磷酸三(2-乙基乙酯)、Brij30[C₁₂H₂₅(OCH₂CH₂)₄OH]、和Brij35[C₁₂H₂₅(OCH₂CH₂)₂₀OH]等。增塑劑可以單獨一種使用，也可兩種以上混合使用。 Exemplarily, the plasticizer includes: phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, and diallyl phthalate, glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, and n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tritolyl phosphate, trixyl phosphate, methyl phosphate, trimethylol ... Phenyl diphenyl phosphate, trixyl phosphate, 2-naphthyl diphenyl phosphate, tolyl di-2,6-xyl phosphate, aromatic condensation phosphate, tris(chloropropyl) phosphate, tris(tribromoneopentyl) phosphate, halogen-containing condensation phosphate, triethylene glycol dioctanoate, triethylene glycol di(2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, dibutyl suberate _, tris(2-ethylethyl) phosphate, Brij30[ _C12H25 ₍ _OCH2CH2 ) _4OH ], and Brij35[ _C12H25 ( _OCH2CH2 ) _20OH ] _, etc. The plasticizer may be used alone or in combination _of two or more.

示例性地，穩定劑包括：氫醌、1,4,4-三甲基-重氮二環(3.2.2)-壬-2-烯-2,3-二氧化物、1-苯基-3-吡唑烷酮、對甲氧基苯酚、烷基和芳基取代的氫醌和醌、叔丁基鄰苯二酚、1,2,3-苯三酚、樹脂酸銅、萘胺、β-萘酚、氯化亞銅、2,6-二叔丁基對甲酚、吩噻嗪、吡啶、硝基苯、二硝基苯、對甲苯醌和氯醌等。穩定劑可以單獨一種使用，也可兩種以上混合使用。 For example, the stabilizer includes: hydroquinone, 1,4,4-trimethyl-diazobicyclo (3.2.2)-non-2-ene-2,3-dioxide, 1-phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinone and quinone, tert-butyl o-catechol, 1,2,3-pyrogallol, copper resinate, naphthylamine, β-naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil, etc. The stabilizer can be used alone or in combination of two or more.

示例性地，塗布助劑包括：丙酮、甲醇、甲基醇、乙基醇、異丙基醇、甲基乙基酮、丙二醇單甲基醚乙酸酯、乳酸乙酯、環己酮、γ-丁內酯、二氯甲烷等。塗布助劑可以單獨一種使用，也可兩種以上混合使用。 Exemplarily, coating aids include: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, γ-butyrolactone, dichloromethane, etc. Coating aids can be used alone or in combination of two or more.

示例性地，剝離促進劑包括：苯磺酸、甲苯磺酸、二甲苯磺酸、苯酚磺酸，甲基、丙基、庚基、辛基、癸基、十二烷基等烷基苯磺酸等。剝離促進劑可以單獨一種使用，也可兩種以上混合使用。 Exemplarily, the stripping accelerator includes: benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl and other alkylbenzenesulfonic acids, etc. The stripping accelerator can be used alone or in combination of two or more.

在100質量份的感光性樹脂組合物中，所述其它助劑的含量為0-10質量份，較佳0.5-5質量份。 In 100 parts by mass of the photosensitive resin composition, the content of the other additives is 0-10 parts by mass, preferably 0.5-5 parts by mass.

<乾膜和濕膜應用><Dry film and wet film applications>

從確保感光性樹脂組合物及其乾膜具有優異的分辨率和色相穩定性的角度考慮，本發明的感光性樹脂組合物的儲存溫度以在-20℃至40℃之間為宜。 From the perspective of ensuring that the photosensitive resin composition and its dry film have excellent resolution and color stability, the storage temperature of the photosensitive resin composition of the present invention is preferably between -20°C and 40°C.

本發明的感光性樹脂組合物可以製備成乾膜，即感光性樹脂層疊體，並應用於印刷電路板、保護圖案、導體圖案、引框線、半導體封裝的製造中，經過不同的工序在不同的基材上形成所需要的圖案。 The photosensitive resin composition of the present invention can be prepared into a dry film, i.e. a photosensitive resin layer stack, and applied in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages, and the required patterns are formed on different substrates through different processes.

本發明的感光性樹脂組合物也可以通過濕膜塗布機塗布至各對應製造步驟中對應的基材上，即作為濕膜應用於印刷電路板、保護圖案、導體圖案、引框線、半導體封裝的製造中，經過不同的工序在不同的基材上形成所需要的圖案。 The photosensitive resin composition of the present invention can also be applied to the corresponding substrate in each corresponding manufacturing step by a wet film coating machine, that is, it can be used as a wet film in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages, and the required patterns can be formed on different substrates through different processes.

乾膜應用 Dry film application

本發明的乾膜即感光性樹脂層疊體，其包含：感光性樹脂組合物形成的感光性樹脂層以及支撐該感光性樹脂層的支撐體。 The dry film of the present invention is a photosensitive resin layer stack, which includes: a photosensitive resin layer formed by a photosensitive resin composition and a support body supporting the photosensitive resin layer.

通常，乾膜的製作包括：將感光性樹脂組合物塗布在支撐體上，乾燥以形成感光性樹脂層；任選地，根據需要貼合覆蓋膜(保護層)。較佳地，乾燥條件是60-100℃下乾燥0.5-15min。感光性樹脂層的厚度較佳為5-95μm，再較佳為10-50μm，更佳為15-30μm。若感光性樹脂層的厚度小於5μm，則絕緣性不佳，而若感光性樹脂層的厚度超過95μm，則解析度可能會較差。 Generally, the preparation of dry film includes: applying a photosensitive resin composition on a support, drying to form a photosensitive resin layer; optionally, laminating a cover film (protective layer) as needed. Preferably, the drying condition is 60-100°C for 0.5-15min. The thickness of the photosensitive resin layer is preferably 5-95μm, more preferably 10-50μm, and more preferably 15-30μm. If the thickness of the photosensitive resin layer is less than 5μm, the insulation is poor, and if the thickness of the photosensitive resin layer exceeds 95μm, the resolution may be poor.

作為支撐體，具體實例可以是各種類型的塑膠膜，如聚對苯二甲酸乙二醇酯、聚乙烯萘二酸酯、聚丙烯、聚乙烯、纖維素乙酸酯、聚甲基丙烯酸烷酯、甲基丙烯酸酯共聚物、聚氯乙烯、聚乙烯醇、聚碳酸酯、聚苯乙烯、玻璃紙、氯乙烯共聚物、聚醯胺、聚亞醯胺、乙烯氯-乙酸乙烯酯共聚物、聚四氟乙烯、聚三氟乙烯及其相似物。此外，亦可使用由兩種或以上材料所組成的複合材料。較佳地，使用的是具有極佳光穿透性的聚對苯二甲酸乙二醇酯。支撐體的厚度較佳為5-150μm，更佳為10-50μm。 As a support, specific examples can be various types of plastic films, such as polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, polyalkyl methacrylate, methacrylate copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, vinyl chloride copolymer, polyamide, polyimide, ethylene chloride-vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene and the like. In addition, a composite material composed of two or more materials can also be used. Preferably, polyethylene terephthalate with excellent light transmittance is used. The thickness of the support is preferably 5-150μm, more preferably 10-50μm.

對感光性樹脂組合物的塗布並無特殊限制，例如可使用噴塗法、滾筒式塗布法、旋轉式塗布法、狹縫式塗布法、壓縮塗布法、簾塗法、染料塗布法、線條塗布法、刮刀塗布法、輥塗法、刮塗法、噴塗法、浸塗法等常規方法。 There is no particular limitation on the coating of the photosensitive resin composition. For example, conventional methods such as spray coating, drum coating, rotary coating, slit coating, compression coating, curtain coating, dye coating, line coating, blade coating, roller coating, scraper coating, spray coating, and dipping coating can be used.

進一步地，本發明提供上述乾膜在製造印刷電路板中的應用，包括： Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of printed circuit boards, including:

(1)層疊工序：將感光性樹脂層疊體層疊於覆銅層疊板或柔性基板上； (1) Lamination process: stacking the photosensitive resin layer on the copper-clad laminate or flexible substrate;

(2)曝光工序：對感光性樹脂層疊體中的感光性樹脂層進行曝光，以圖像狀照射活性光線使曝光部分進行光固化； (2) Exposure process: exposing the photosensitive resin layer in the photosensitive resin layer stack, irradiating the active light in an image-like manner to photo-cure the exposed part;

(3)顯影工序：將感光性樹脂層的未曝光部分用顯影液去除，以形成保護圖案； (3) Development process: remove the unexposed part of the photosensitive resin layer with a developer to form a protective pattern;

(4)導體圖案形成工序：對覆銅層疊板或柔性基板表面的未被保護圖案覆蓋的部分進行刻蝕或鍍覆； (4) Conductor pattern forming process: etching or plating the portion of the copper-clad laminate or flexible substrate surface not covered by the protective pattern;

(5)剝離工序：將保護圖案從該覆銅層疊板或柔性基板剝離。 (5) Peeling process: peeling the protective pattern from the copper-clad laminate or flexible substrate.

進一步地，本發明提供上述乾膜在製造保護圖案中的應用，包括如上所述的層疊工序、曝光工序和顯影工序，不同在於：層疊工序中感光性樹脂層疊體可層疊於各種不同材質的基板上。 Furthermore, the present invention provides the application of the above-mentioned dry film in the manufacture of protective patterns, including the lamination process, exposure process and development process as described above, the difference being that in the lamination process, the photosensitive resin layer stack can be laminated on substrates of various materials.

進一步地，本發明提供上述乾膜在製造導體圖案中的應用，包括如上所述的層疊工序、曝光工序、顯影工序和導體圖案形成工序，不同在於：層疊工序中感光性樹脂層疊體層疊於金屬板或金屬覆膜絕緣板上。 Furthermore, the present invention provides the application of the above dry film in manufacturing a conductor pattern, including the lamination process, exposure process, development process and conductor pattern forming process as described above, except that: in the lamination process, the photosensitive resin layer is laminated on a metal plate or a metal-coated insulating plate.

進一步地，本發明提供上述乾膜在製造引框線中的應用，包括如上所述的層疊工序、曝光工序、顯影工序、和導體圖案形成工序，不同在於：層疊工序中感光性樹脂層疊體層疊於金屬板上，導體圖案形成工序中對未被保護圖案覆蓋的部分進行刻蝕。 Furthermore, the present invention provides the application of the above dry film in manufacturing lead frame wires, including the above-mentioned lamination process, exposure process, development process, and conductor pattern forming process, except that: In the lamination process, the photosensitive resin layer is laminated on the metal plate, and in the conductor pattern forming process, the portion not covered by the protective pattern is etched.

進一步地，本發明提供上述乾膜在製造半導體封裝中的應用，包括如上所述的層疊工序、曝光工序、顯影工序、和導體圖案形成工序，不同在於：層疊工序中感光性樹脂層疊體層疊於具有大規模集成電路的晶片上，導體圖案形成工序中對未被保護圖案覆蓋的部分進行鍍覆。 Furthermore, the present invention provides the application of the above dry film in the manufacture of semiconductor packaging, including the above-mentioned lamination process, exposure process, development process, and conductor pattern forming process, the difference being that: in the lamination process, the photosensitive resin layer is laminated on a chip with a large-scale integrated circuit, and in the conductor pattern forming process, the portion not covered by the protective pattern is coated.

濕膜應用 Wet film applications

本發明的感光性樹脂組合物可以濕膜方式直接塗布在基板上使用，以用於印刷電路板、保護圖案、導體圖案、引框線、半導體封裝等的製造。 The photosensitive resin composition of the present invention can be directly coated on a substrate in a wet film manner for use in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packages, etc.

非限制性地，可利用輥塗、刮塗、噴塗、浸塗等常規方法將感光性樹脂組合物塗布於基板上，乾燥後形成感光性樹脂層。 Without limitation, the photosensitive resin composition can be applied to the substrate by conventional methods such as roller coating, scraper coating, spray coating, and dip coating, and a photosensitive resin layer is formed after drying.

在基板上形成感光性樹脂層後，後續工序如曝光工序、顯影工序、導體圖案形成工序和剝離工序，均可參照乾膜應用的方式進行。 After forming a photosensitive resin layer on the substrate, subsequent processes such as exposure process, development process, conductor pattern formation process and stripping process can be carried out in the same way as dry film application.

曝光工序中，曝光可以列舉出掩模曝光法(佈線圖的負或正掩模圖形將活性光線呈圖像狀地照射的方法)、投影曝光法，也可以採用通過激光直接成像曝光法、數字光學處理曝光法等直接描畫曝光法將活性光線呈圖像狀地照射的方法。作為活性光線的光源，可使用公知的光源，如碳弧燈、汞蒸氣弧燈、超高壓示燈、高壓示燈、氙燈、氬氣激光等氣體激光、YAG激光等固體激光、半導體激光和氮化鎵系藍紫色激光等有效放射出紫外線的光源。此外，還可以使用照相用泛光燈、日光燈等有效放射出可見光的光源。本發明的感光性樹脂組合物對活性光線的光源種類沒有特別限制，曝光量較佳為10-1000mJ/cm²。 In the exposure process, the exposure may be performed by a mask exposure method (a method in which a negative or positive mask pattern of a wiring pattern is irradiated with active light in an image-like manner), a projection exposure method, or a method in which active light is irradiated in an image-like manner by a direct drawing exposure method such as a laser direct imaging exposure method or a digital optical processing exposure method. As a light source for active light, a known light source may be used, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure indicator lamp, a high pressure indicator lamp, a xenon lamp, a gas laser such as an argon laser, a solid laser such as a YAG laser, a semiconductor laser, and a gallium nitride-based blue-violet laser, etc., which effectively radiates ultraviolet light. In addition, a light source that effectively radiates visible light such as a floodlight for photography and a fluorescent lamp may be used. The photosensitive resin composition of the present invention has no particular limitation on the type of active light source, and the exposure amount is preferably 10-1000 mJ/cm ² .

顯影工序中，將感光性樹脂層的未曝光部分用顯影液去除。在感光性樹脂層上存在支撐體的情況下，可利用自動剝離器等先除去支撐體，然後再使用鹼性水溶液、水系顯影液、有機溶劑等顯影液除去未曝光部分。鹼性水溶液的例子可以是0.1-5質量%的碳酸鈉溶液、0.1-5質量%的碳酸鉀溶液、0.1-5質量%的氫氧化鈉溶液等，pH值較佳為9-11。鹼性水溶液中還可以加入表面活性劑、消泡劑、有機溶劑等。顯影的方式可以是浸漬、噴霧、刷洗等常規方式。 In the developing process, the unexposed part of the photosensitive resin layer is removed with a developer. If there is a support on the photosensitive resin layer, the support can be removed first by using an automatic stripper, and then an alkaline aqueous solution, an aqueous developer, an organic solvent or other developer can be used to remove the unexposed part. Examples of alkaline aqueous solutions can be 0.1-5 mass% sodium carbonate solution, 0.1-5 mass% potassium carbonate solution, 0.1-5 mass% sodium hydroxide solution, etc., and the pH value is preferably 9-11. Surfactants, defoaming agents, organic solvents, etc. can also be added to the alkaline aqueous solution. The developing method can be conventional methods such as immersion, spraying, and brushing.

刻蝕處理中，以形成於基板上的抗蝕圖案(即保護圖案)作為掩模，將未被覆蓋的電路形成用基板的導體層刻蝕除去，從而形成導體圖案。刻蝕處理的方法可以根據待去除的導體層而選擇。例如，作為蝕刻液可以列舉出氧化銅溶液、氧化鐵溶液、鹼蝕刻溶液、過氧化氫系蝕刻液等。 In the etching process, the conductive layer of the circuit forming substrate that is not covered is etched away using the anti-etching pattern (i.e., protective pattern) formed on the substrate as a mask, thereby forming a conductive pattern. The etching process method can be selected according to the conductive layer to be removed. For example, as etching solutions, copper oxide solutions, iron oxide solutions, alkaline etching solutions, hydrogen peroxide etching solutions, etc. can be listed.

鍍敷處理中，以形成於基板上的抗蝕圖案為掩模，在未被覆蓋的電路形成用基板的絕緣板上鍍覆銅和焊錫等。鍍敷處理後，除去抗蝕圖案從而形成導體圖案。作為鍍敷處理的方法，既可以是電鍍處理，也可以是無電解鍍覆處理，較佳無電解鍍覆處理。作為無電解鍍覆處理，可以列舉出：硫酸銅鍍敷和焦磷酸銅鍍敷等銅鍍敷、高均勻焊錫(high-throw solder)鍍敷等焊錫鍍敷、瓦特浴(硫酸鎳-氯化鎳)鍍敷和氨基磺酸鎳鍍敷等鎳鍍敷、硬質金鍍敷和軟質金鍍敷等金鍍敷。 In the plating process, copper, solder, etc. are plated on the insulating plate of the circuit forming substrate which is not covered, using the anti-etching pattern formed on the substrate as a mask. After the plating process, the anti-etching pattern is removed to form a conductor pattern. The plating process can be either electroplating or electroless plating, and electroless plating is preferred. As electroless plating treatment, there can be listed: copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, nickel plating such as Watt bath (nickel sulfate-nickel chloride) plating and nickel sulfamate plating, gold plating such as hard gold plating and soft gold plating.

抗蝕圖案的除去可以通過比顯影工序中使用的鹼性水溶液鹼性更強的水溶液來進行剝離。作為強鹼性水溶液的實例，可使用例如1-10質量%的氫氧化鈉水溶液。 The removal of the anti-corrosion pattern can be performed by using an aqueous solution with a stronger alkalinity than the alkaline aqueous solution used in the development process. As an example of a strongly alkaline aqueous solution, a 1-10 mass% sodium hydroxide aqueous solution can be used.

圖1是產物a1的高效液相色譜圖。 Figure 1 is a high performance liquid chromatogram of product a1.

圖2是產物a2的高效液相色譜圖。 Figure 2 is the HPLC chromatogram of product a2.

圖3是1-2’位BCIM的單晶衍射圖。 Figure 3 is the single crystal diffraction pattern of BCIM at the 1-2’ position.

圖4是2’-3位BCIM的單晶衍射圖。 Figure 4 is the single crystal diffraction pattern of 2’-3 BCIM.

圖5是1-5’位BCIM的單晶衍射圖。 Figure 5 is the single crystal diffraction pattern of BCIM at the 1-5’ position.

圖6是1-4’位BCIM的單晶衍射圖。 Figure 6 is the single crystal diffraction pattern of BCIM at the 1-4’ position.

圖7是1-2’位BCIM的XRD分析譜圖。 Figure 7 is the XRD analysis spectrum of 1-2’ BCIM.

圖8是2’-3位BCIM的XRD分析譜圖。 Figure 8 is the XRD analysis spectrum of 2’-3 BCIM.

圖9是產物a2的XRD分析譜圖。 Figure 9 is the XRD analysis spectrum of product a2.

以下將結合具體實施例對本發明作進一步詳細說明，但不應將其理解為對本發明保護範圍的限制。 The present invention will be further described in detail below in conjunction with specific embodiments, but they should not be construed as limiting the scope of protection of the present invention.

1.BCIM混合光引發劑的製備1. Preparation of BCIM Mixed Photoinitiator

1.1 BCIM混合光引發劑a1、a2的製備 1.1 Preparation of BCIM mixed photoinitiators a1 and a2

氮氣保護下，向10L的反應釜中投入976g的2-(鄰氯苯基)-4,5-二苯基咪唑(INC)、20g的30%液鹼、10g的四丁基溴化銨和6000g的甲苯，加熱攪拌，並在內溫60℃時滴加500g的次氯酸鈉(11%的水溶液)，滴加結束後保溫反應，取樣通過HPLC中控，至INC小於1%，反應完全，結束保溫。保溫反應結束後，用1000g純水洗滌四次，然後用1000g甲苯萃取一次水層，將有機層進行減壓蒸餾至溶劑完全蒸乾，加入1000g甲醇，攪拌過濾、淋洗、烘乾，得到933g產物a1。使用高效液相色譜儀對產物a1進行檢測。附圖1是產物a1的高效液相色譜圖，顯示產物a1中1-2’位BCIM和2’-3位BCIM佔比95.61%，1-4’位BCIM和1-5’位BCIM佔比1.69%，其他連接位BCIM佔比0.97%。 Under nitrogen protection, 976g of 2-(o-chlorophenyl)-4,5-diphenylimidazole (INC), 20g of 30% liquid alkali, 10g of tetrabutylammonium bromide and 6000g of toluene were added to a 10L reactor, heated and stirred, and 500g of sodium hypochlorite (11% aqueous solution) was added dropwise at an internal temperature of 60°C. After the addition was completed, the reaction was kept warm, and a sample was taken for central control by HPLC until INC was less than 1%, indicating that the reaction was complete, and the insulation was terminated. After the insulation reaction was completed, the mixture was washed four times with 1000g of pure water, and then the aqueous layer was extracted once with 1000g of toluene. The organic layer was distilled under reduced pressure until the solvent was completely evaporated, 1000g of methanol was added, and the mixture was stirred, filtered, rinsed, and dried to obtain 933g of product a1. Product a1 was detected using a high performance liquid chromatograph. Figure 1 is a high performance liquid chromatogram of product a1, showing that BCIM at positions 1-2' and 2'-3 accounted for 95.61% of product a1, BCIM at positions 1-4' and 1-5' accounted for 1.69%, and BCIM at other connecting positions accounted for 0.97%.

氮氣保護下，向5000mL的四口燒瓶中投入500g的產物a1和3000g的甲苯，內溫60℃加熱攪拌至溶清，然後減壓蒸餾至剩餘約800g甲苯後，降溫至25℃，過濾、淋洗、烘乾，得到432g產物a2。使用高效液相色譜儀對產物a2進行檢測。附圖2是產物a2的高效液相色譜圖，顯示產物a2中1-2’位BCIM和2’-3位BCIM佔比99.55%，1-4’位BCIM和1-5’位BCIM佔比0.33%。 Under nitrogen protection, 500g of product a1 and 3000g of toluene were added to a 5000mL four-necked flask, heated and stirred at an internal temperature of 60°C until dissolved, then distilled under reduced pressure until about 800g of toluene remained, cooled to 25°C, filtered, rinsed, and dried to obtain 432g of product a2. Product a2 was detected using a high performance liquid chromatograph. Figure 2 is a high performance liquid chromatogram of product a2, showing that 1-2' BCIM and 2'-3 BCIM accounted for 99.55% of product a2, and 1-4' BCIM and 1-5' BCIM accounted for 0.33%.

1.2 BCIM混合光引發劑各組分的分離及表徵 1.2 Separation and characterization of components of BCIM mixed photoinitiator

在此，首先闡述BCIM反應生成的機制：三芳基咪唑分子中氮原子失去H原子而帶負電荷，鄰氯苯基的存在使得三芳基咪唑中2-位的C更活潑，電荷效應使得2-位的C原子帶正電荷，所以帶負電荷的N原子進攻帶正電荷的C原子，最後電子轉移，生成BCIM。具體反應機制歷程如下所示： Here, we first explain the mechanism of BCIM reaction generation: the nitrogen atom in the triarylimidazole molecule loses the H atom and becomes negatively charged. The presence of the o-chlorophenyl group makes the 2-position C in the triarylimidazole more active. The charge effect makes the 2-position C atom positively charged, so the negatively charged N atom attacks the positively charged C atom, and finally the electron is transferred to generate BCIM. The specific reaction mechanism process is as follows:

依據BCIM的反應機制，BCIM應是由1-2’、1’-2、2-3’和2’-3這四種連接位構成的雙咪唑化合物，由於INC是對稱結構，所以1-2’和1’-2是同一個結構，2-3’和2’-3是同一個結構。故而，BCIM應是由1-2’和2’-3這兩種連接位構成的雙咪唑化合物，其組成分別為：1-2’位BCIM：2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑；2’-3位BCIM：2,2’-二(鄰氯苯基)-4,4’,5,5’-四苯基-2’,3-二咪唑。結構如式(Ⅳ)和(Ⅴ)所示。 According to the reaction mechanism of BCIM, BCIM should be a biimidazole compound composed of four connecting positions: 1-2', 1'-2, 2-3' and 2'-3. Since INC is a symmetrical structure, 1-2' and 1'-2 are the same structure, and 2-3' and 2'-3 are the same structure. Therefore, BCIM should be a biimidazole compound composed of two connecting positions: 1-2' and 2'-3. Its components are: 1-2' BCIM: 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-diimidazole; 2'-3 BCIM: 2,2'-di(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole. The structures are shown in formulas (Ⅳ) and (Ⅴ).

雖然鄰氯苯基的存在使得三芳基咪唑中2-位的C更活潑，同樣的，電荷效應也可以使得4-位的C和5-位的C原子帶正電荷，生成1-5’位BCIM和1-4’位BCIM。 Although the presence of o-chlorophenyl makes the 2-position C in triarylimidazole more active, similarly, the charge effect can also make the 4-position C and 5-position C atoms positively charged, generating 1-5' BCIM and 1-4' BCIM.

1-5’位BCIM的具體反應機制歷程如下所示： The specific reaction mechanism of 1-5' BCIM is as follows:

1-4’位BCIM的具體反應機制歷程如下所示： The specific reaction mechanism of 1-4' BCIM is as follows:

為了精確驗證產物的結構組成，通過柱層析、色譜分離、單晶分離等現有公知技術手段，分別得到純的1-2’位BCIM、2’-3位BCIM、1-4’位BCIM、1-5’位BCIM。附圖3是1-2’位BCIM的單晶衍射圖，附圖4是2’-3位BCIM的單晶衍射圖，附圖5是1-5’位BCIM的單晶衍射圖，附圖6是1-4’位BCIM的單晶衍射圖。 In order to accurately verify the structural composition of the product, pure 1-2' BCIM, 2'-3 BCIM, 1-4' BCIM, and 1-5' BCIM were obtained by existing known technical means such as column analysis, chromatographic separation, and single crystal separation. Figure 3 is a single crystal diffraction pattern of 1-2' BCIM, Figure 4 is a single crystal diffraction pattern of 2'-3 BCIM, Figure 5 is a single crystal diffraction pattern of 1-5' BCIM, and Figure 6 is a single crystal diffraction pattern of 1-4' BCIM.

為了更形象的表徵1-2’位BCIM和2’-3位BCIM，將1-2’位BCIM、2’-3位BCIM和產物a2分別進行了粉末XRD分析。圖7是1-2’位BCIM的XRD分析譜圖，圖8是2’-3位BCIM的XRD分析譜圖，圖9是產物a2的XRD分析譜圖。從圖7-9可以形象的看出，產物a2主要是由1-2’位BCIM和2’-3位BCIM混合組成，且1-2’位BCIM的含量高於2’-3位BCIM。其他連接位的BCIM含量極少，因此在XRD譜圖中沒有明顯的衍射峰顯現。 In order to more vividly characterize 1-2' BCIM and 2'-3 BCIM, powder XRD analysis was performed on 1-2' BCIM, 2'-3 BCIM and product a2. Figure 7 is the XRD analysis spectrum of 1-2' BCIM, Figure 8 is the XRD analysis spectrum of 2'-3 BCIM, and Figure 9 is the XRD analysis spectrum of product a2. It can be seen from Figures 7-9 that product a2 is mainly composed of a mixture of 1-2' BCIM and 2'-3 BCIM, and the content of 1-2' BCIM is higher than that of 2'-3 BCIM. The content of BCIM at other connection positions is very small, so there is no obvious diffraction peak in the XRD spectrum.

1.3 感光度測試 1.3 Sensitivity test

參照表1中所示的配方，制得感光性樹脂組合物以進行感光度測試，表中各物質用量單位均為g。 Referring to the formula shown in Table 1, a photosensitive resin composition was prepared for sensitivity testing. The unit of dosage of each substance in the table is g.

表1

Table 1

上述表1中，雙季戊四醇六丙烯酸酯(DPHA)採購於天津市北聯精細化學品開發有限公司，隱色結晶紫(LCV)採購于常州強力電子新材料股份有限公司，N-苯基甘氨酸(NPG)採購於深圳市鵬順興科技有限公司，丙二醇甲醚醋酸酯(PGMEA)採購於濟南滙豐達化工有限公司。 In Table 1 above, dipentaerythritol hexaacrylate (DPHA) was purchased from Tianjin Beilian Fine Chemicals Development Co., Ltd., hidden crystal violet (LCV) was purchased from Changzhou Qiangli Electronic New Materials Co., Ltd., N-phenylglycine (NPG) was purchased from Shenzhen Pengshunxing Technology Co., Ltd., and propylene glycol methyl ether acetate (PGMEA) was purchased from Jinan Huifengda Chemical Co., Ltd.

將感光性樹脂組合物充分攪拌，使用棒塗布器將組合物均勻塗布于作為支撐體的25μm厚的聚對苯二甲酸乙二醇酯薄膜的表面上。在烘箱中95℃乾燥5min，形成感光性樹脂層。通過Stouffer21階曝光尺進行曝光，帶有高壓水銀燈的曝光機(

一

社制，商品名EXM-1201)，以60mJ/cm²的照射能量曝光感光層。曝光後，以30℃的1質量%碳酸鈉水溶液用最少顯影時間的2倍的時間噴射顯影，除去未曝光部分，進行顯影。然後，通過測定形成的光固化膜的階段曝光尺的格數，來評價感光性樹脂組合物的光敏度。光敏度用階段曝光尺的格數表示，該階段曝光尺的格數越高，表示光敏度高，結果如表2所示。 The photosensitive resin composition was stirred thoroughly and evenly applied on the surface of a 25 μm thick polyethylene terephthalate film as a support using a rod coater. The film was dried in an oven at 95°C for 5 minutes to form a photosensitive resin layer. The film was exposed using a Stouffer 21-step exposure ruler and an exposure machine with a high-pressure mercury lamp (

one

The photosensitive layer was exposed to 60 mJ/ ^cm2 of irradiation energy using a 1 mass% sodium carbonate aqueous solution at 30°C for twice the minimum development time. The unexposed portion was removed and developed. Then, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of grids of the stage exposure scale of the photocured film formed. The photosensitivity is expressed by the number of grids of the stage exposure scale. The higher the number of grids of the stage exposure scale, the higher the photosensitivity. The results are shown in Table 2.

表2

Table 2

產物a2與1-2’位BCIM、2’-3位BCIM的感光度一致，1-4’位BCIM、1-5’位BCIM的感光度一致。但是1-4’位BCIM和1-5’位BCIM由於其結構本身位阻大於1-2’位BCIM和2’-3位BCIM，裂解需要的能量低於1-2’位BCIM和2’-3位BCIM，故而顯示出更高的感度。但是由於其裂解需要的能量較低，所以表現出較差的穩定性。 The sensitivity of product a2 is consistent with that of 1-2' BCIM and 2'-3 BCIM, and that of 1-4' BCIM and 1-5' BCIM. However, 1-4' BCIM and 1-5' BCIM have higher steric hindrance than 1-2' BCIM and 2'-3 BCIM, and the energy required for cleavage is lower than that of 1-2' BCIM and 2'-3 BCIM, so they show higher sensitivity. However, since the energy required for cleavage is lower, they show poor stability.

1.4 BCIM混合光引發劑a3-a11的製備 1.4 Preparation of BCIM mixed photoinitiators a3-a11

a3：分離得到的1-2’位BCIM單晶； a3: The separated 1-2' BCIM single crystal;

a4：分離得到的2’-3位BCIM單晶； a4: The separated 2’-3 BCIM single crystal;

a5：通過複配，得到組分為50%的1-2’位BCIM、50%的2’-3位BCIM的混合物； a5: Through compounding, a mixture of 50% 1-2' BCIM and 50% 2'-3 BCIM is obtained;

a6：通過複配，得到組分為49%的1-2’位BCIM、50%的2’-3位BCIM、0.5%的1-4’位BCIM、0.5%的1-5’位BCIM的混合物； a6: Through compounding, a mixture of 49% 1-2' BCIM, 50% 2'-3' BCIM, 0.5% 1-4' BCIM, and 0.5% 1-5' BCIM is obtained;

a7：通過複配，得到組分為47%的1-2’位BCIM、50%的2’-3位BCIM、3%的1-4’位BCIM的混合物； a7: Through compounding, a mixture of 47% 1-2' BCIM, 50% 2'-3' BCIM, and 3% 1-4' BCIM is obtained;

a8：通過複配，得到組分為47%的1-2’位BCIM、50%的2’-3位BCIM、3%的1-5’位BCIM的混合物； a8: Through compounding, a mixture of 47% 1-2' BCIM, 50% 2'-3' BCIM, and 3% 1-5' BCIM is obtained;

a9：通過複配，得到組分為48%的1-2’位BCIM、47%的2’-3位BCIM、2.5%的1-4’位BCIM、2.5%的1-5’位BCIM的混合物； a9: Through compounding, a mixture of 48% 1-2' BCIM, 47% 2'-3 BCIM, 2.5% 1-4' BCIM, and 2.5% 1-5' BCIM was obtained;

a10：通過複配，得到組分為48%的1-2’位BCIM、47%的2’-3位BCIM、5%的1-4’位BCIM； a10: Through compounding, the components obtained are 48% 1-2' BCIM, 47% 2'-3' BCIM, and 5% 1-4' BCIM;

a11：通過複配，得到組分為48%的1-2’位BCIM、47%的2’-3位BCIM、5%的1-5’位BCIM。 a11: Through compounding, the components obtained are 48% 1-2' BCIM, 47% 2'-3' BCIM, and 5% 1-5' BCIM.

2.感光性樹脂組合物的製備2. Preparation of photosensitive resin composition

參照表3中所示配方，將各組分混合均勻制得感光性樹脂組合物。如無特別說明，表3中所示份數均為質量份。 Referring to the formula shown in Table 3, the components are mixed evenly to prepare a photosensitive resin composition. Unless otherwise specified, the parts shown in Table 3 are parts by mass.

表3

table 3

表3中各組分代號表示的含義如表4中所示。 The meaning of each component code in Table 3 is shown in Table 4.

表4

Table 4

鹼可溶性聚合物B的製備：在氮氣氛圍下，向配有攪拌器、回流冷卻器、溫度計和滴液漏斗的燒瓶中，加入甲基溶纖劑和甲苯(質量比3：2)的混合溶劑500g，攪拌加熱至80℃後，將甲基丙烯酸100g、甲基丙烯酸乙酯200g、丙烯酸乙酯100g、苯乙烯100g和偶氮雙異丁腈0.8g混合制得的溶液慢慢滴加至燒瓶中，滴加時間為4小時，滴加結束後繼續反應2小時。接著，向燒瓶內滴加溶解有1.2g偶氮雙異丁腈的混合溶劑(組成同上)100g，滴加時間為10分鐘，滴加結束後，在80℃下進一步反應3小時，再升溫至90℃繼續反應2小時。反應結束後，過濾得到鹼可溶性聚合物B，酸值為196mgKOH/g，重均分子量約為80000。 Preparation of alkali-soluble polymer B: Under a nitrogen atmosphere, 500 g of a mixed solvent of methylcellulose and toluene (mass ratio 3:2) was added to a flask equipped with a stirrer, a reflux cooler, a thermometer and a dropping funnel. After stirring and heating to 80°C, a solution prepared by mixing 100 g of methacrylic acid, 200 g of ethyl methacrylate, 100 g of ethyl acrylate, 100 g of styrene and 0.8 g of azobisisobutyronitrile was slowly dripped into the flask for 4 hours. After the dripping was completed, the reaction was continued for 2 hours. Then, 100g of a mixed solvent (same composition as above) containing 1.2g of azobisisobutyronitrile was added dropwise into the flask for 10 minutes. After the addition, the mixture was further reacted at 80°C for 3 hours, and then the temperature was raised to 90°C for another 2 hours. After the reaction, alkali-soluble polymer B was obtained by filtration, with an acid value of 196mgKOH/g and a weight-average molecular weight of about 80,000.

3.性能評價3. Performance evaluation

3.1 評價方式 3.1 Evaluation method

<乾膜的製作> <Dry film production>

將感光性樹脂組合物充分攪拌，使用棒塗器將其均勻塗布在作為支撐體的25μm厚的聚對苯二甲酸乙二醇酯薄膜的表面上，在乾燥機中95℃乾燥5分鐘，形成厚度為40μm的感光性樹脂層，然後在感光性樹脂層的沒有層壓聚對苯二甲酸乙二醇酯薄膜的表面貼合作為保護層的15μm厚的聚乙烯薄膜，獲得乾膜。 The photosensitive resin composition was fully stirred and evenly applied on the surface of a 25μm thick polyethylene terephthalate film as a support using a rod coater. It was dried in a dryer at 95°C for 5 minutes to form a 40μm thick photosensitive resin layer. A 15μm thick polyethylene film as a protective layer was then laminated on the surface of the photosensitive resin layer without the polyethylene terephthalate film laminated thereon to obtain a dry film.

<基板表面整平> <Substrate surface leveling>

作為基板，使用層壓有35μm厚的軋製銅箔的1.2mm厚的覆銅層壓板，對表面進行濕式拋光輥研磨[3M公司製造的Scotch-Brite(註冊商標)HD#600，通過兩次]。 As a substrate, a 1.2 mm thick copper-clad laminated with a 35 μm thick rolled copper foil was used, and the surface was wet-polished with a polishing roll [Scotch-Brite (registered trademark) HD#600 manufactured by 3M, passed twice].

<層壓> <Layer pressure>

將聚乙烯薄膜保護層從乾膜上剝離，然後使用熱輥層壓機(旭化成製造的AL-70)，以105℃的輥溫度將其層壓於預熱至60℃的覆銅層壓板上。氣體壓力為0.35MPa，層壓速度為1.5m/min。 The polyethylene film protective layer was peeled off from the dry film and then laminated onto the copper-clad press plate preheated to 60°C at a roll temperature of 105°C using a hot roll laminating press (AL-70 manufactured by Asahi Kasei). The gas pressure was 0.35MPa and the laminating speed was 1.5m/min.

<曝光> <Exposure>

將掩膜放置在作為支撐體的聚對苯二甲酸乙二醇酯薄膜上，通過超高壓汞燈(ORCMANUFACTURINGCO.，LTD.製造的HMW-201KB)，以60mJ/cm²的照射能量曝光感光層。 The mask was placed on a polyethylene terephthalate film as a support, and the photosensitive layer was exposed with an ultra-high pressure mercury lamp (HMW-201KB manufactured by ORC MANUFACTURING CO., LTD.) at an irradiation energy of 60 mJ/ ^cm2 .

<顯影> <Image>

剝離聚對苯二甲酸乙二醇酯薄膜，使用鹼顯影機(FujiKikoCo.，Ltd.製造的乾膜用顯影機)，將30℃的1質量%的Na₂CO₃水溶液噴霧在感光性樹脂層上，用2倍於最小顯影時間的時間溶解除去感光性樹脂層的未曝光部分。以未曝光部分的感光性樹脂層完全溶解所需的最短時間為最小顯影時間。 Peel off the polyethylene terephthalate film, use an alkaline developer (developer for dry films manufactured by Fuji Kiko Co., Ltd.), spray a 1 mass % Na ₂ CO ₃ aqueous solution at 30°C on the photosensitive resin layer, and dissolve and remove the unexposed portion of the photosensitive resin layer for twice the minimum developing time. The shortest time required for the unexposed portion of the photosensitive resin layer to completely dissolve is the minimum developing time.

3.2 評價內容 3.2 Evaluation Content

(1)分辨率 (1) Resolution

利用具有Line/Space=10：10-150：150(單位：μm)的佈線圖案的光掩模進行曝光顯影後，測量乾膜的分辨率。分辨率是在曝光後顯影形成的抗蝕圖案中，未曝光部分被清除乾淨後的圖案的最小值。評價基準如下所述： The resolution of the dry film is measured after exposure and development using a photomask with a wiring pattern of Line/Space=10:10-150:150 (unit: μm). The resolution is the minimum value of the pattern after the unexposed part of the anti-etching pattern formed by development after exposure is cleared. The evaluation criteria are as follows:

○：分辨率值在30μm以下； ○: Resolution value is below 30μm;

◎：分辨率值在30μm-50μm，不包括端值； ◎: Resolution value is 30μm-50μm, excluding end value;

×：分辨率值在50μm以上。 ×: The resolution value is above 50μm.

(2)保持時間分辨率 (2) Maintaining time resolution

將乾膜在23℃、50%濕度的環境下，在暗處儲存2周，然後通過與上述分辨率試驗同樣的方法評價分辨率。 The dried film was stored in a dark place at 23°C and 50% humidity for 2 weeks, and then the resolution was evaluated by the same method as the above resolution test.

(3)色相穩定性評價 (3) Hue stability evaluation

從感光性樹脂層壓體剝離聚乙烯薄膜，使用UV-vis光譜儀(島津製作所(株)製造，UV-240)，測定波長600nm光的透過率。此時，在光譜儀的參照側放入與該感光性樹脂層壓體中使用的相同的聚對苯二甲酸乙二酯薄膜，將源自聚對苯二甲酸乙二酯薄膜的透過率作為空白值。 The polyethylene film was peeled off from the photosensitive resin laminate, and the transmittance of light with a wavelength of 600 nm was measured using a UV-vis spectrometer (manufactured by Shimadzu Corporation, UV-240). At this time, a polyethylene terephthalate film identical to that used in the photosensitive resin laminate was placed on the reference side of the spectrometer, and the transmittance derived from the polyethylene terephthalate film was used as the blank value.

將使用溫度-20-40℃下保存3天后的感光性樹脂組合物溶液製作的感光性樹脂層疊體，與使用保存前的感光性樹脂組合物溶液製作的感光性樹脂層疊體的透光率進行比較，基於它們的差如下地分級。 The transmittance of the photosensitive resin layer stack made from the photosensitive resin composition solution stored at -20-40°C for 3 days was compared with that of the photosensitive resin layer stack made from the photosensitive resin composition solution before storage, and the transmittance was graded as follows based on the difference.

○：600nm下的透過率的差的絕對值小於1%； ○: The absolute value of the difference in transmittance at 600nm is less than 1%;

◎：600nm下的透過率的差的絕對值為1%以上且小於5%； ◎: The absolute value of the difference in transmittance at 600nm is greater than 1% and less than 5%;

×：600nm下的透過率的差的絕對值為5%以上。 ×: The absolute value of the difference in transmittance at 600nm is 5% or more.

(4)曝光前後色相穩定性評價 (4) Evaluation of hue stability before and after exposure

感光性樹脂組合物溶液製作的感光性樹脂層疊體曝光前，用愛色麗X-rite(上海凱得色彩管理有限公司)色差儀中的透射方法，測試感光性樹脂組合物溶液製作的感光性樹脂層疊體曝光前的色度即L、a、b值。將感光性樹脂組合物溶液製作的感光性樹脂層疊體用60mJ/cm²的照射能量進行曝光，感光性樹脂組合物溶液製作的感光性樹脂層疊體的曝光後，同樣用色差儀中透射的方法，以感光性樹脂組合物溶液製作的感光性樹脂層疊體曝光前的色度為測量標準，對比測試曝光後感光性樹脂組合物溶液製作的感光性樹脂層疊體的的L、a、b及ΔL、Δa、Δb、ΔE值。基於它們的差如下地分級。 Before the photosensitive resin layer stack made of the photosensitive resin composition solution is exposed, the chromaticity, i.e., L, a, and b values of the photosensitive resin layer stack made of the photosensitive resin composition solution before exposure are tested using the transmission method in an X-Rite (Shanghai Kaide Color Management Co., Ltd.) colorimeter. The photosensitive resin layer stack made of the photosensitive resin composition solution was exposed to 60 mJ/ ^cm2 of irradiation energy. After the exposure, the L, a, b and ΔL, Δa, Δb, ΔE values of the photosensitive resin layer stack made of the photosensitive resin composition solution after the exposure were measured by the colorimeter transmission method, with the chromaticity of the photosensitive resin layer stack made of the photosensitive resin composition solution before exposure as the measurement standard. The values were graded as follows based on their differences.

○：ΔE小於5； ○: ΔE is less than 5;

◎：ΔE為5以上且小於10； ◎: ΔE is greater than 5 and less than 10;

×：ΔE為10以上。 ×: ΔE is 10 or more.

3.3 評價結果 3.3 Evaluation results

評價結果如表5中所示。 The evaluation results are shown in Table 5.

表5

table 5

本發明的感光性樹脂組合物及其乾膜具有優異的分辨率和色相穩定性，即使長時間儲存後也不會有分辨率下降的趨勢。該感光性樹脂組合物能夠以乾膜和濕膜的方式在製造印刷電路板、保護圖案、導體圖案、引框線、半導體封裝等方面得到廣泛應用。 The photosensitive resin composition and its dry film of the present invention have excellent resolution and color stability, and there is no tendency of resolution reduction even after long-term storage. The photosensitive resin composition can be widely used in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, semiconductor packaging, etc. in the form of dry films and wet films.

上述實施例為本發明較佳的實施方式，但本發明的實施方式並不受上述實施例的限制，其它的任何未背離本發明的精神實質與原理下所作的改變、修飾、替代、組合、簡化，均應為等效的置換方式，都包含在本發明的保護範圍之內。 The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principle of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims

其中，具有1-4’連接位的式(Ⅱ)化合物和具有1-5’連接位的式(Ⅲ)化合物的含量之和佔該混合光引發劑的0.33%以下，且具有1-2’連接位的式(Ⅳ)化合物和具有2’-3連接位的式(V)化合物的含量之和佔該混合光引發劑的99.55%以上，

式(Ⅲ)

其中，當該組分(A)的混合光引發劑包含式(Ⅳ)和式(V)兩種化合物時，式(Ⅳ)化合物的含量小於或等於式(V)化合物的含量；(B)鹼可溶性聚合物；(C)具有烯屬不飽和雙鍵的化合物；(D)供氫體；以及(E)任選地，其它助劑。 A photosensitive resin composition with improved system color stability comprises the following components: (A) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole mixed photoinitiator, the structure of which is shown in formula (I),

The total content of the compound of formula (II) having a 1-4' linking position and the compound of formula (III) having a 1-5' linking position accounts for less than 0.33% of the mixed photoinitiator, and the total content of the compound of formula (IV) having a 1-2' linking position and the compound of formula (V) having a 2'-3 linking position accounts for more than 99.55% of the mixed photoinitiator.

Formula (III)

Wherein, when the mixed photoinitiator of component (A) contains two compounds of formula (IV) and formula (V), the content of the compound of formula (IV) is less than or equal to the content of the compound of formula (V); (B) an alkali-soluble polymer; (C) a compound having an olefinic unsaturated double bond; (D) a hydrogen donor; and (E) optionally, other auxiliary agents.

如請求項1所述的感光性樹脂組合物，其中所述的鹼可溶性聚合物選自(甲基)丙烯酸系聚合物、苯乙烯系聚合物、環氧系聚合物、脂肪族聚氨酯(甲基)丙烯酸酯聚合物、芳香族聚氨酯(甲基)丙烯酸酯聚合物、醯胺系樹脂、醯胺環氧系樹脂、醇酸系樹脂以及酚醛系樹脂中的一種或兩種以上的組合。 The photosensitive resin composition as described in claim 1, wherein the alkali-soluble polymer is selected from one or a combination of two or more of (meth)acrylic polymers, styrene polymers, epoxy polymers, aliphatic polyurethane (meth)acrylate polymers, aromatic polyurethane (meth)acrylate polymers, amide resins, amide epoxy resins, alkyd resins and phenolic resins.

如請求項2所述的感光性樹脂組合物，其中所述的鹼可溶性聚合物選自含羧基的鹼可溶性聚合物。 The photosensitive resin composition as described in claim 2, wherein the alkali-soluble polymer is selected from carboxyl-containing alkali-soluble polymers.

如請求項3所述的感光性樹脂組合物，其中所述的鹼可溶性聚合物選自由(甲基)丙烯酸酯、乙烯性不飽和羧酸和其它可共聚單體共聚而成的(甲基)丙烯酸酯系聚合物。 The photosensitive resin composition as described in claim 3, wherein the alkali-soluble polymer is selected from (meth)acrylate polymers obtained by copolymerization of (meth)acrylate, ethylenically unsaturated carboxylic acid and other copolymerizable monomers.

如請求項1所述的感光性樹脂組合物，其中所述的具有烯屬不飽和雙鍵的化合物選自α,β-不飽和羧酸與多元醇反應而得的化合物、雙酚A類(甲基)丙烯酸酯化合物、α,β-不飽和羧酸與含縮水甘油基的化合物反應而得的化合物、分子內具有氨酯鍵的(甲基)丙烯酸酯化合物、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羥基丙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、β-羥基乙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、β-羥基丙基-β’-(甲基)丙烯醯氧基乙基-鄰苯二甲酸酯、苯二甲酸類化合物、及(甲基)丙烯酸烷基酯中的一種或兩種以上的組合。 The photosensitive resin composition as described in claim 1, wherein the compound having an olefinic unsaturated double bond is selected from a compound obtained by reacting an α,β-unsaturated carboxylic acid with a polyol, a bisphenol A-type (meth)acrylate compound, a compound obtained by reacting an α,β-unsaturated carboxylic acid with a compound containing a glycidyl group, a (meth)acrylate compound having an urethane bond in the molecule, nonylphenoxy polyvinyloxy acrylate, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxyethyl-β'-(meth)acryloyloxyethyl-phthalate, β-hydroxypropyl-β'-(meth)acryloyloxyethyl-phthalate, phthalic acid compounds, and a combination of one or more of the following: alkyl (meth)acrylates.

如請求項5所述的感光性樹脂組合物，其中所述的具有烯屬不飽和雙鍵的化合物選自雙酚A類(甲基)丙烯酸酯化合物和分子內具有氨酯鍵的(甲基)丙烯酸酯化合物中的一種或兩種以上的組合。 The photosensitive resin composition as described in claim 5, wherein the compound having an olefinic unsaturated double bond is selected from one or a combination of two or more of bisphenol A type (meth)acrylate compounds and (meth)acrylate compounds having an urethane bond in the molecule.

如請求項1所述的感光性樹脂組合物，其中所述的供氫體選自胺類化合物、羧酸類化合物、含有巰基的有機硫化合物和醇類化合物中的一種或兩種以上的組合。 The photosensitive resin composition as described in claim 1, wherein the hydrogen donor is selected from one or a combination of two or more of amine compounds, carboxylic acid compounds, organic sulfur compounds containing alkyl groups and alcohol compounds.

如請求項1-7中任一項所述的感光性樹脂組合物，其中所述的的感光性樹脂組合物的儲存溫度在-20℃至40℃之間。 A photosensitive resin composition as described in any one of claims 1 to 7, wherein the storage temperature of the photosensitive resin composition is between -20°C and 40°C.

一種感光性樹脂層疊體，包含：如請求項1-8中任一項所述的感光性樹脂組合物形成的感光性樹脂層以及支撐該感光性樹脂層的支撐體。 A photosensitive resin layer stack, comprising: a photosensitive resin layer formed by the photosensitive resin composition as described in any one of claims 1 to 8 and a support body supporting the photosensitive resin layer.

如請求項1-8中任一項所述的感光性樹脂組合物、以及請求項9所述的感光性樹脂層疊體在製造印刷電路板、保護圖案、導體圖案、引框線、半導體封裝中的應用。 Application of the photosensitive resin composition as described in any one of claims 1 to 8 and the photosensitive resin layer stack as described in claim 9 in the manufacture of printed circuit boards, protective patterns, conductor patterns, lead wires, and semiconductor packages.