TW201437245A - Epoxy acrylate resin and manufacturing method thereof, acid anhydride adduct of epoxy acrylate, curable resin composition, alkali developable photosensitive resin composition and cured product thereof - Google Patents
Epoxy acrylate resin and manufacturing method thereof, acid anhydride adduct of epoxy acrylate, curable resin composition, alkali developable photosensitive resin composition and cured product thereof Download PDFInfo
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本發明涉及一種可以形成顯影性優異、並且密接性、焊料耐熱性也優異的硬化物的環氧丙烯酸酯樹脂、環氧丙烯酸酯酸酐加成物、使用這些的硬化性樹脂組成物、鹼顯影型感光性樹脂組成物及其硬化物,可以適用於:印刷配線板的保護層(overcoat)、底塗層、絕緣層等永久保護膜,防焊油墨(solder resist ink),增層基板的相關絕緣材料等,或適於製造印刷配線板、特別是可撓性印刷配線板的可以利用稀鹼溶液顯影的防焊油墨等。 The present invention relates to an epoxy acrylate resin, an epoxy acrylate anhydride adduct, a curable resin composition using the same, and an alkali-developable type, which are excellent in developability and excellent in adhesion and solder heat resistance. The photosensitive resin composition and the cured product thereof can be applied to: a protective film (overcoat) of a printed wiring board, a permanent protective film such as an undercoat layer, an insulating layer, a solder resist ink, and an insulating layer of a build-up substrate. A material or the like, or a solder resist ink which can be used for producing a printed wiring board, particularly a flexible printed wiring board, which can be developed with a dilute alkali solution.
從防焊油墨用於印刷配線板的露出的導體電路的絕緣保護被膜用途及防止焊料附著於電路的焊料不需要的部分的用途的觀點來看,塗膜形成法通常利用網版印刷法進行塗佈,並對硬化被膜要求焊料耐熱性、耐濕性、密接性、耐化學品性、耐鍍敷性、耐電解腐蝕性。所述類型的阻焊劑有熱硬化型與紫外線硬化型這二種,前者主要使用環氧樹脂,後者大多 使用環氧丙烯酸酯樹脂。但是,近年來由於各種印刷配線板中的導體電路圖案的微細化與位置精度提高、以及安裝零件的進一步小型化,而利用阻焊劑的絕緣被膜形成變為網版印刷法,通過光法的圖像形成正成為主流。 另外,利用光法的抗蝕劑的顯影先前使用有機溶劑,但從大氣污染或安全性的觀點來看,期望使用稀鹼水溶液。由於此種背景,阻焊劑產生利用先前的網版印刷對應的環氧樹脂或環氧丙烯酸酯樹脂而無法令人滿意的問題。 From the viewpoint of the use of the solder resist ink for the insulating protective film of the exposed conductor circuit of the printed wiring board and the use of the portion where the solder is not required to adhere to the solder of the circuit, the coating film forming method is usually applied by screen printing. The cloth and the hardened film are required to have solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. The types of solder resists are thermosetting type and ultraviolet curing type. The former mainly uses epoxy resin, and the latter mostly An epoxy acrylate resin is used. However, in recent years, the miniaturization of the conductor circuit pattern in various printed wiring boards, the improvement in positional accuracy, and the further miniaturization of the mounted components have led to the formation of an insulating film using a solder resist to a screen printing method. Image formation is becoming mainstream. Further, the development of the resist by the photo method has previously used an organic solvent, but from the viewpoint of air pollution or safety, it is desirable to use a dilute aqueous alkali solution. Due to this background, the solder resist produces an unsatisfactory problem using the epoxy or epoxy acrylate resin corresponding to the previous screen printing.
對於光法及稀鹼水溶液顯影的應對,例如已知:苯酚酚醛清漆型 環氧丙烯酸酯樹脂或雙酚A環氧丙烯酸酯樹脂、或通過這些環氧丙烯酸酯樹脂與酸二酐的反應而得的半酯化物等(專利文獻1、專利文獻2)。但是,在使用這些公知的環氧丙烯酸酯樹脂或其酸酐改質物作為阻焊劑用樹脂組成物時,雖然滿足稀鹼水溶液的顯影性,但為了使物性穩定而需要硬化溫度至少為180℃以上,不僅加熱設備花費成本,而且例如在核心基板使用玻璃環氧基板時,有硬化溫度過高而引起基板的變色或翹曲的擔心。而且,由這些公知的環氧丙烯酸酯樹脂或其酸酐改質物而得的硬化被膜,存在焊料耐熱性、耐濕性、密接性、耐化學品性、耐鍍敷性、耐電解腐蝕性等不充分的問題。 For the photo method and the development of a dilute alkali aqueous solution, for example, a phenol novolak type is known. An epoxy acrylate resin, a bisphenol A epoxy acrylate resin, or a half esterified product obtained by the reaction of these epoxy acrylate resin and acid dianhydride (Patent Document 1 and Patent Document 2). However, when such a known epoxy acrylate resin or an anhydride modified product thereof is used as a resin composition for a solder resist, the developability of a dilute alkali aqueous solution is satisfied, but the curing temperature is required to be at least 180 ° C or more in order to stabilize physical properties. Not only is the cost of the heating device expensive, but also, for example, when the glass epoxy substrate is used for the core substrate, there is a fear that the curing temperature is too high to cause discoloration or warpage of the substrate. Further, the cured film obtained from these known epoxy acrylate resins or their anhydride-modified materials has solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. Full question.
近年來,伴隨著印刷配線板的高密度化,對於多晶片模組(Multichip Module,MCM)用增層基板或晶片尺寸封裝(Chip Scale Package,CSP)等晶片安裝基板用絕緣層,要求可靠性與耐高壓鍋性或耐熱循環性,在將所述公知的環氧丙烯酸酯樹脂或其酸酐改質物作為阻焊劑用樹脂組成物時,也存在無法發揮出充分的可靠性的問題。 In recent years, with the increase in density of printed wiring boards, it is required to mount an insulating layer for a wafer such as a build-up substrate or a chip scale package (CSP) for a multi-chip module (MCM). When the known epoxy acrylate resin or its anhydride modified product is used as a resin composition for a solder resist, the above-mentioned known epoxy acrylate resin or heat-resistant cycle property may have a problem that sufficient reliability cannot be exhibited.
如此,從基板材料的耐熱性的制約或製造設備等的觀點來看,無法實現低溫硬化,無法實現通過光法利用稀鹼水的顯影,且無法充分地滿足印刷配線板的阻焊劑所需要的焊料耐熱性、耐濕性、密接性、耐化學品性、耐鍍敷性、耐電解腐蝕性、以及MCM等高密度安裝基板等的絕緣層硬化膜所要求的可靠性。另外,已知經芳香族改質的苯酚酚醛清漆型環氧樹脂,但並未研究鹼顯影性樹脂組成物或其硬化物(專利文獻3)。 As described above, from the viewpoint of heat resistance of the substrate material, manufacturing equipment, and the like, low-temperature curing cannot be achieved, development of the diluted alkali water by the photo method cannot be achieved, and the solder resist of the printed wiring board cannot be sufficiently satisfied. Solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, electrolytic corrosion resistance, and reliability required for an insulating layer cured film such as a high-density mounting substrate such as MCM. Further, an aromatically modified phenol novolac type epoxy resin is known, but an alkali-developable resin composition or a cured product thereof has not been studied (Patent Document 3).
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開昭61-243869號公報 [Patent Document 1] Japanese Patent Laid-Open No. 61-243869
[專利文獻2]日本專利特開2003-026762號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-026762
[專利文獻3]日本專利特開2010-235819號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-235819
因此,本發明的目的在於提供一種可以實現光或熱硬化的新穎的環氧丙烯酸酯樹脂及其酸酐加成物,並且提供一種可以實現160℃以下的低溫硬化與可以實現通過光法利用稀鹼水的顯影的硬化性樹脂、及將其作為主要的樹脂成分的硬化性樹脂組成物。另外,本發明的目的在於提供一種印刷配線板的阻焊劑或絕緣膜等所需要的顯影性、焊料耐熱性、塗膜硬度、密接性、耐化學品性等可靠性優異的硬化性樹脂組成物及其硬化物。 Accordingly, it is an object of the present invention to provide a novel epoxy acrylate resin and an anhydride adduct thereof which can achieve light or heat hardening, and provide a low temperature hardening which can achieve a temperature below 160 ° C and a utilization of a light alkali by photo method A curable resin for developing water and a curable resin composition which is a main resin component. In addition, it is an object of the present invention to provide a curable resin composition which is excellent in reliability such as developability, solder heat resistance, coating film hardness, adhesion, and chemical resistance required for a solder resist or an insulating film of a printed wiring board. And its hardened material.
本發明是一種環氧丙烯酸酯樹脂,其由下述通式(1)表示:[化1]
(此處,R1表示氫或碳數1~6的烴基,R2表示下述式(a)所示的芳烷基,R6表示氫或甲基,n表示1~20的數;另外,p表示0.1~2.5的數)
(此處,R3~R5表示氫原子或碳數1~6的烴基)。 (here, R 3 to R 5 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms).
另外,本發明是所述的環氧丙烯酸酯樹脂,其中所述通式(a)為源自苯乙烯的芳烷基。 Further, the present invention is the epoxy acrylate resin, wherein the general formula (a) is an aralkyl group derived from styrene.
而且,本發明是一種所述的環氧丙烯酸酯樹脂的製造方法,其特徵在於:使(甲基)丙烯酸與下述通式(2)所示的環氧樹脂反應;
(此處,G表示縮水甘油基,R1、R2、n及p與通式(1)同義)。 (H Here, G represents a glycidyl group, and R 1 , R 2 , n and p are synonymous with the general formula (1)).
另外,本發明是一種環氧丙烯酸酯酸酐加成物,其由下述通式(3)表示,其特徵在於:使多元酸化合物與所述的環氧丙烯酸酯樹脂反應而得;
(此處,R1、R2、R6、n、p與通式(1)同義,X表示氫或-OC-A(COOH)m所示的多元酸基,A為多元酸的殘基,X的10莫耳%以上為所述多元酸基;m表示1、2或3)。 (here, R 1 , R 2 , R 6 , n, p are synonymous with the formula (1), X represents hydrogen or a polybasic acid group represented by -OC-A(COOH) m , and A is a residue of a polybasic acid More than 10 mol% of X is the polybasic acid group; m represents 1, 2 or 3).
另外,本發明是一種硬化性樹脂組成物,其含有所述的環氧丙烯酸酯樹脂或環氧丙烯酸酯酸酐加成物、及聚合起始劑。 Further, the present invention is a curable resin composition comprising the above epoxy acrylate resin, epoxy acrylate anhydride adduct, and a polymerization initiator.
而且,本發明是一種鹼顯影型感光性樹脂組成物,其含有所述的環氧丙烯酸酯酸酐加成物與光聚合起始劑,而且所述的鹼顯影型感光性樹脂組成物,其中更含有環氧樹脂。 Furthermore, the present invention is an alkali-developable photosensitive resin composition comprising the above-described epoxy acrylate anhydride adduct and a photopolymerization initiator, and the alkali-developable photosensitive resin composition, among which Contains epoxy resin.
另外,本發明是一種硬化物,其使所述的硬化性樹脂組成物或鹼顯影型感光性樹脂組成物硬化而成。 Further, the present invention is a cured product obtained by curing the curable resin composition or the alkali-developable photosensitive resin composition.
根據本發明,可以形成能够利用光或熱實現硬化的新穎的環氧丙烯酸酯樹脂與其酸酐加成物,包含環氧丙烯酸酯樹脂或酸酐加成物的樹脂組成物可以實現160℃以下的低溫硬化、及通過光法利用稀鹼水的顯影,且 焊料耐熱性、塗膜硬度、密接性、耐化學品性等增層基板的絕緣層等所要求的可靠性優異,因此不僅適於印刷配線板的阻焊劑,而且適合作為增層基板或CSP等的晶片安裝基板用層間絕緣膜的材料。 According to the present invention, a novel epoxy acrylate resin capable of hardening by light or heat and an acid anhydride adduct thereof can be formed, and a resin composition containing an epoxy acrylate resin or an acid anhydride adduct can achieve low temperature hardening at 160 ° C or lower. And the development of dilute alkali water by photofabrication, and It is excellent in reliability required for insulating layers such as solder heat resistance, coating film hardness, adhesion, and chemical resistance, and is therefore suitable not only as a solder resist for printed wiring boards, but also as a build-up substrate or CSP. The material of the interlayer insulating film for the wafer mounting substrate.
圖1是環氧丙烯酸酯樹脂的凝膠滲透層析法(Gel Permeation Chromatography,GPC)圖表。 1 is a gel permeation Chromatography (GPC) chart of an epoxy acrylate resin.
圖2是酸酐加成物的GPC圖表。 Figure 2 is a GPC chart of an acid anhydride adduct.
以下,對本發明進行詳細地說明。 Hereinafter, the present invention will be described in detail.
本發明的環氧丙烯酸酯樹脂是所述通式(1)所示的化合物,可為n=1的單一化合物,也可以是包含n為不同的成分的寡聚物。平均的重複數n(數量平均)為1~20、優選為1~5。 The epoxy acrylate resin of the present invention is a compound represented by the above formula (1), and may be a single compound of n = 1, or may be an oligomer containing n different components. The average number of repetitions n (number average) is 1 to 20, preferably 1 to 5.
在通式(1)中,R1表示氫或碳數1~6的烴基。R1優選氫或碳數1~6的烷基或苯基,更優選氫。R6為氫或甲基。 In the formula (1), R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. R 1 is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably hydrogen. R 6 is hydrogen or methyl.
R2表示所述式(a)所示的芳烷基。R3~R5表示氫原子或碳數1~6的烴基。R3優選氫或碳數1~6的烷基或苯基,更優選氫。R4~R5優選氫或碳數1~6的烷基,更優選氫或甲基。R4~R5可以相同也可以不同,在一個為烴基時,優選另一個為氫。p平均表示0.1~2.5的數、優選表示0.2~2.0、更優選表示0.3~1.5的數。此處,平均是指式(a)的芳烷基R2所鍵結的每1個苯環中所存在的R2的數量的平均。 R 2 represents the aralkyl group represented by the formula (a). R 3 to R 5 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 3 is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably hydrogen. R 4 to R 5 are preferably hydrogen or an alkyl group having 1 to 6 carbon atoms, more preferably hydrogen or methyl. R 4 to R 5 may be the same or different, and when one is a hydrocarbon group, the other is preferably hydrogen. The average value of p represents a number from 0.1 to 2.5, preferably from 0.2 to 2.0, more preferably from 0.3 to 1.5. Here, the average refers to an average of the number of R 2 present per one benzene ring to which the aralkyl group R 2 of the formula (a) is bonded.
通式(1)的環氧丙烯酸酯樹脂的合成法並無限制,首先,優選由酚類與甲醛類合成酚醛清漆型酚樹脂或二羥基苯基甲烷類(將這些稱為 酚樹脂類),並利用芳烷基化劑將所述酚樹脂類進行芳烷基化。然後,優選使經芳烷基化的酚樹脂類與表氯醇反應,而製成使OH基成為縮水甘油醚基的通式(2)的環氧樹脂,並使其與(甲基)丙烯酸類反應的方法。但是,可以將酚類進行芳烷基化,並且也可以製成環氧樹脂後進行芳烷基化。另外,在與表氯醇反應而製成環氧樹脂時,有環氧基開環生成少量的聚合而成的結構成分,但也可以混入所述成分。 The method for synthesizing the epoxy acrylate resin of the formula (1) is not limited. First, it is preferred to synthesize a novolac type phenol resin or a dihydroxyphenylmethane from a phenol and a formaldehyde (referred to as these The phenol resin is aralkylated by an aralkylating agent. Then, it is preferred to react an aralkylated phenol resin with epichlorohydrin to form an epoxy resin of the formula (2) in which an OH group is a glycidyl ether group, and to make it with (meth)acrylic acid. The method of class reaction. However, the phenols may be aralkylated, and may also be formed into an epoxy resin for aralkylation. Further, when an epoxy resin is produced by reacting with epichlorohydrin, an epoxy group is opened to form a small amount of a structural component obtained by polymerization, but the component may be mixed.
芳烷基化有利的是使用如苯乙烯類的芳香族烯烴、或如苄氯或苄醇的芳烷基鹵化物或芳烷基醇作為芳烷基化劑,在酸催化劑的存在下進行。在使用苯乙烯時,R2成為α-甲基苄基,在使用苄氯時,R2成為苄基。 The aralkylation is advantageously carried out using an aromatic olefin such as a styrene or an aralkyl halide or an aralkyl alcohol such as benzyl chloride or benzyl alcohol as an aralkylating agent in the presence of an acid catalyst. When styrene is used, R 2 becomes an α-methylbenzyl group, and when benzyl chloride is used, R 2 becomes a benzyl group.
將酚樹脂類或經芳烷基化的酚樹脂類製成環氧樹脂的反應為公 知的,可以採用這些公知的反應。有利的是使用過量的表氯醇,在鹼催化劑的存在下進行反應的方法。例如可以採用由酚醛清漆型酚樹脂製造酚醛清漆型環氧樹脂的方法。並且,通過使經芳烷基化的酚樹脂類與表氯醇反應,而可以獲得通式(2)的環氧樹脂。另外,通式(2)所示的環氧樹脂揭示於日本專利特開2010-235819號公報或世界專利WO2012/043213號等中。 The reaction of making phenolic resin or aralkylated phenolic resin into epoxy resin is public It is known that these well-known reactions can be employed. Advantageously, a method of carrying out the reaction in the presence of a base catalyst using an excess of epichlorohydrin. For example, a method of producing a novolac type epoxy resin from a novolac type phenol resin can be employed. Further, an epoxy resin of the formula (2) can be obtained by reacting an aralkylated phenol resin with epichlorohydrin. Further, the epoxy resin represented by the formula (2) is disclosed in Japanese Patent Laid-Open No. 2010-235819 or World Patent No. WO2012/043213.
本發明的環氧丙烯酸酯樹脂由通式(1)表示。通式(1)的環氧丙烯酸酯樹脂可以使通式(2)的環氧樹脂、與(甲基)丙烯酸(是指丙烯酸、甲基丙烯酸或這兩者)反應而製造。此處,(甲基)丙烯酸中,優選為丙烯酸。另外,可以並用丙烯酸與甲基丙烯酸。反應通常在50℃~150℃的範圍內在1小時~20小時的範圍內進行。環氧樹脂與(甲基)丙烯酸的使用比例,能够以環氧基與羧基的莫耳比為等莫耳比、或其附近(優選為0.8~1.2)的方式 使用。 The epoxy acrylate resin of the present invention is represented by the general formula (1). The epoxy acrylate resin of the formula (1) can be produced by reacting an epoxy resin of the formula (2) with (meth)acrylic acid (referred to as acrylic acid, methacrylic acid or both). Here, among (meth)acrylic acid, acrylic acid is preferable. In addition, acrylic acid and methacrylic acid can be used in combination. The reaction is usually carried out in the range of from 50 ° C to 150 ° C in the range of from 1 hour to 20 hours. The ratio of use of the epoxy resin to (meth)acrylic acid can be such that the molar ratio of the epoxy group to the carboxyl group is equal to or higher than the molar ratio, or in the vicinity thereof (preferably 0.8 to 1.2). use.
本發明的環氧丙烯酸酯酸酐加成物由所述通式(3)表示。在通 式(3)中X表示氫或-OC-A(COOH)m所示的多元酸基。A為多元酸的殘基,m表示1、2或3。通式(3)的環氧丙烯酸酯酸酐加成物可以通過使通式(1)的環氧丙烯酸酯樹脂、A(COOH)m+1所示的多元酸或其衍生物、優選其酸酐反應而得。以下,將多元酸或其衍生物稱為酸酐類。 The epoxy acrylate anhydride adduct of the present invention is represented by the above formula (3). In the formula (3), X represents hydrogen or a polybasic acid group represented by -OC-A(COOH) m . A is a residue of a polybasic acid, and m represents 1, 2 or 3. The epoxy acrylate anhydride adduct of the formula (3) can be obtained by reacting an epoxy acrylate resin of the formula (1), a polybasic acid represented by A(COOH) m+1 or a derivative thereof, preferably an acid anhydride thereof. And got it. Hereinafter, a polybasic acid or a derivative thereof is referred to as an acid anhydride.
在通式(1)、通式(2)及通式(3)中,只要無特別說明,共通的符號具有相同含義。 In the general formula (1), the general formula (2), and the general formula (3), the common symbols have the same meaning unless otherwise specified.
通式(1)的環氧丙烯酸酯樹脂與酸酐類的反應典型的是指利用 酸酐類將通式(1)中的OH基進行酯化的反應。在通式(3)中,X無須全部相同,在一分子中可以具有氫或多元酸基,並非全部為氫。優選X的10莫耳%以上、更優選20莫耳%~100莫耳%為所述多元酸基,在X的90莫耳%以上、有利的是100莫耳%為多元酸基時,可以形成更優選的硬化性樹脂。多元酸基與鹼為反應性,因此可以對酐加成物或其部分聚合反應物(未硬化物)賦予鹼可溶性。通過改變X中的多元酸基的存在比,而可以調整鹼可溶性,並可以使鹼顯影性最佳化。 The reaction of the epoxy acrylate resin of the formula (1) with an acid anhydride typically refers to utilization. An acid anhydride is a reaction in which an OH group in the formula (1) is esterified. In the general formula (3), X does not need to be all the same, and may have hydrogen or a polybasic acid group in one molecule, and not all of them are hydrogen. Preferably, 10 mol% or more, more preferably 20 mol% to 100 mol% of X is the polybasic acid group, and when 90 mol% or more of X, and advantageously 100 mol% is a polybasic acid group, A more preferable curable resin is formed. Since the polybasic acid group is reactive with the base, it is possible to impart alkali solubility to the anhydride adduct or a partial polymerization reaction product (uncured product). By changing the existence ratio of the polybasic acid groups in X, the alkali solubility can be adjusted, and the alkali developability can be optimized.
酐加成物可以使環氧丙烯酸酯樹脂、與酸二酐或酸單酐等酸酐類 反應而製造。另外,酸酐類也可以是偏苯三甲酸酐等,偏苯三甲酸酐為酸單酐。 Anhydride adducts can be used to make epoxy acrylate resins, acid anhydrides or acid anhydrides Manufactured by reaction. Further, the acid anhydride may be trimellitic anhydride or the like, and the trimellitic anhydride is an acid monoanhydride.
優選的酸酐由下述式(4)表示。 A preferred acid anhydride is represented by the following formula (4).
[O(CO)2]pA(COOH)q (4) [O(CO) 2 ] p A(COOH) q (4)
(其中,A表示芳香族或脂肪族的多元酸的殘基,可以具有取代基。p為1或2,q為0或1,2p+q為2~4。) (wherein A represents a residue of an aromatic or aliphatic polybasic acid, and may have a substituent. p is 1 or 2, q is 0 or 1, and 2p+q is 2 to 4.)
酸二酐可以列舉:二苯醚四甲酸酐、二苯基碸四甲酸酐、聯苯四甲酸酐、萘四甲酸酐、蒽四甲酸酐、菲四甲酸酐、六氟亞異丙基雙(鄰苯二甲酸酐)、乙二醇雙(脫水偏苯三甲酸酯)、甲基環己烯四甲酸酐、四甲基二矽氧烷四甲酸酐等。優選列舉:聯苯四甲酸酐、二苯醚四甲酸酐、均苯四甲酸酐、二苯甲酮四甲酸酐。 Examples of the acid dianhydride include diphenyl ether tetracarboxylic anhydride, diphenylsulfonium tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, naphthalene tetracarboxylic anhydride, perylenetetracarboxylic anhydride, phenanthrene anhydride, and hexafluoroisopropylidene ( Phthalic anhydride), ethylene glycol bis(dehydrated trimellitate), methylcyclohexene tetracarboxylic anhydride, tetramethyldioxane tetracarboxylic anhydride, and the like. Preferably, it is biphenyltetracarboxylic anhydride, diphenyl ether tetracarboxylic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride.
酸單酐例如有:順丁烯二酸酐、琥珀酸酐、衣康酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基納迪克酸酐、十二炔基琥珀酸酐、氯茵酸酐、偏苯三甲酸酐。優選列舉:四氫鄰苯二甲酸酐。 The acid monoanhydrides are, for example, maleic anhydride, succinic anhydride, itaconic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydroortho Phthalic anhydride, methyl nadic anhydride, dodecynyl succinic anhydride, chlorinic anhydride, trimellitic anhydride. Preferably, tetrahydrophthalic anhydride is used.
在通式(3)中,為了獲得X為單一的酸酐加成物,代表性的是通過使1種酸酐類與通式(1)所示的環氧丙烯酸酯樹脂進行理論量反應而得。為了獲得X不同的酸酐加成物,可以通過使2種以上的酸酐類反應、或使理論量以下的多元酸與環氧丙烯酸酯樹脂的H反應而得。例如,多元酸也可以並用酸單酐與酸二酐,有利的是將優選X的10莫耳%以上、更優選20莫耳%~100莫耳%、尤其優選40莫耳%~80莫耳%設為多元酸基,由酸單酐與酸二酐生成的多元酸基的比例(酸單酐/酸二酐)可以設為10/90~90/10左右。另外,在使用酸二酐時,有通式(1)中的多個羥基與酸二酐反應而形成寡聚物的情況,但所述寡聚物也為本發明的酸酐加成物。 In the general formula (3), in order to obtain a single acid anhydride adduct of X, it is typically obtained by subjecting one type of acid anhydride to a theoretical amount of the epoxy acrylate resin represented by the formula (1). In order to obtain an acid anhydride addition product different in X, it can be obtained by reacting two or more kinds of acid anhydrides or by reacting a polybasic acid having a theoretical amount or less with H of an epoxy acrylate resin. For example, the polybasic acid may also be used in combination with an acid monoanhydride and an acid dianhydride, and it is advantageous to preferably have 10 mol% or more of X, more preferably 20 mol% to 100 mol%, particularly preferably 40 mol% to 80 mol%. The % is a polybasic acid group, and the ratio of the polybasic acid group formed by the acid monoanhydride to the acid dianhydride (acid monoanhydride/acid dianhydride) can be set to about 10/90 to 90/10. Further, when an acid dianhydride is used, a plurality of hydroxyl groups in the formula (1) are reacted with an acid dianhydride to form an oligomer, but the oligomer is also an acid anhydride adduct of the present invention.
通過在本發明的環氧丙烯酸酯樹脂及環氧丙烯酸酯酸酐加成物中調配光聚合起始劑或自由基聚合起始劑,而可以獲得本發明的硬化性樹 脂組成物或鹼顯影型感光性樹脂組成物。此外,調配多官能丙烯酸酯也有利。本發明的樹脂組成物中的樹脂成分(樹脂及硬化後成為樹脂的成分)的30重量%以上、優選為50重量%以上、更優選為70重量%以上,可以為本發明的環氧丙烯酸酯或酸酐加成物。另外,稱為本發明的樹脂組成物時,只要無特別說明,是以包括硬化性樹脂組成物及鹼顯影型感光性樹脂組成物這兩者的含義使用,但上下文明確時,表示任一種。並且,調配了環氧丙烯酸酯酸酐加成物的樹脂組成物為鹼顯影型感光性樹脂組成物,調配了環氧丙烯酸酯樹脂的樹脂組成物為硬化性樹脂組成物,調配了這兩者的樹脂組成物為硬化性樹脂組成物或鹼顯影型感光性樹脂組成物。另外,調配了環氧丙烯酸酯酸酐加成物的樹脂組成物、及鹼顯影型感光性樹脂組成物也表現出硬化性,因此有成為硬化性樹脂組成物的情況。另外,通式(1)、與通式(3)中,僅通式(1)中的OH基的一部分或全部被取代成OX的不同也可以稱為不同,因此是將兩者的樹脂、酸酐加成物總稱的含義,且也稱為本發明的樹脂。 The curable tree of the present invention can be obtained by blending a photopolymerization initiator or a radical polymerization initiator in the epoxy acrylate resin and the epoxy acrylate anhydride adduct of the present invention. A lipid composition or an alkali-developable photosensitive resin composition. In addition, it is also advantageous to formulate multifunctional acrylates. 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more of the resin component (resin and resin component after curing) in the resin composition of the present invention may be the epoxy acrylate of the present invention. Or anhydride adduct. In addition, the resin composition of the present invention is used in the sense of including both a curable resin composition and an alkali-developable photosensitive resin composition, unless otherwise specified. Further, the resin composition in which the epoxy acrylate anhydride adduct is blended is an alkali-developable photosensitive resin composition, and the resin composition in which the epoxy acrylate resin is blended is a curable resin composition, and both of them are blended. The resin composition is a curable resin composition or an alkali-developable photosensitive resin composition. In addition, the resin composition in which the epoxy acrylate anhydride adduct is prepared and the alkali-developable photosensitive resin composition also exhibit curability, and thus may be a curable resin composition. Further, in the general formula (1) and the general formula (3), only a part or all of the OH group in the general formula (1) may be referred to as a difference in OX, and therefore, the resin may be Anhydride adducts are collectively referred to and are also referred to as resins of the present invention.
光聚合起始劑可以使用公知的各種光聚合起始劑。優選的光聚合 起始劑例如可以列舉:安息香、苯偶醯、安息香甲醚、安息香異丙醚、苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、1-羥基環己基苯基酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉醇丙烷、N,N-二甲基氨基苯乙酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌、2-戊基蒽醌、2-異丙基噻噸酮、2,4-二甲基噻噸酮、苯乙酮二甲基縮酮、二苯甲酮、4-甲基二苯甲酮、4,4'-二氯二苯甲酮、4,4'-雙二乙基氨基二苯甲酮等。這些可以單獨使用,或混合2種以上而使用。 As the photopolymerization initiator, various known photopolymerization initiators can be used. Preferred photopolymerization Examples of the initiator include benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichlorobenzene. Ethyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinol propane, N,N-dimethylaminoacetophenone, 2- Methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, 2-pentyl hydrazine, 2-isopropyl thioxanthone, 2,4-dimethyl thiophene Tons of ketone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminodiphenyl Ketone and so on. These can be used individually or in mixture of 2 or more types.
相對於通式(3)所示的環氧丙烯酸酯酸酐加成物100重量份,光聚合起始劑的使用量為0重量份~100重量份,優選為0.5重量份~40重量份,更優選為1重量份~10重量份。另外,相對於樹脂組成物100重量份,光聚合起始劑的使用量通常為0重量份~50重量份,優選為1重量份~20重量份。在使用熱聚合起始劑時,可以不使用光聚合起始劑,但本發明的感光性樹脂組成物由於曝光、顯影性優異,因此使用光聚合起始劑來用作光硬化性樹脂組成物較為有利。 The photopolymerization initiator is used in an amount of from 0 part by weight to 100 parts by weight, preferably from 0.5 part by weight to 40 parts by weight, based on 100 parts by weight of the epoxy acrylate anhydride adduct of the formula (3). It is preferably from 1 part by weight to 10 parts by weight. Further, the photopolymerization initiator is used in an amount of usually from 0 part by weight to 50 parts by weight, preferably from 1 part by weight to 20 parts by weight, based on 100 parts by weight of the resin composition. When a thermal polymerization initiator is used, a photopolymerization initiator may not be used. However, since the photosensitive resin composition of the present invention is excellent in exposure and developability, a photopolymerization initiator is used as a photocurable resin composition. More favorable.
而且,可以同時使用這些光聚合起始劑與公知的光增感劑的1種或2種以上。光增感劑例如可以列舉:米其勒酮、N,N-二甲基氨基苯甲酸乙酯、N,N-二甲基氨基苯甲酸異戊酯、三乙醇胺、三乙基胺等。相對於通式(1)所示的化合物100重量份,光增感劑的使用量為0重量份~20重量份,優選為0.02重量份~10重量份,更優選為0.05重量份~2重量份。另外,相對於鹼顯影型感光性樹脂組成物100重量份,光增感劑的使用量通常為0重量份~10重量份,優選為0.01重量份~5重量份。 Further, one or two or more kinds of these photopolymerization initiators and known photo-sensitizers can be used at the same time. Examples of the photosensitizer include michione, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine, and the like. The photosensitizer is used in an amount of from 0 part by weight to 20 parts by weight, preferably from 0.02 part by weight to 10 parts by weight, more preferably from 0.05 part by weight to 2 parts by weight based on 100 parts by weight of the compound of the formula (1). Share. In addition, the amount of the photosensitizer used is usually from 0 part by weight to 10 parts by weight, preferably from 0.01 part by weight to 5 parts by weight, per 100 parts by weight of the alkali-developable photosensitive resin composition.
為了進行熱聚合,優選調配自由基聚合起始劑,在僅進行光硬化 時,也可以不調配。優選的自由基聚合起始劑例如可以例示:公知的過氧化苯甲醯、過氧化對氯苯甲醯、過氧化碳酸二異丙酯、過氧化碳酸二-2-乙基己酯、過氧化特戊酸叔丁酯等過氧化物,及1,1'-偶氮雙環己烷-1-甲腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮雙-(異丁酸甲酯)、α,α-偶氮雙-(異丁腈)、4,4'-偶氮雙-(4-氰基戊酸)等偶氮化合物等。相對於通式(1)所示的化合物100重量份,熱聚合起始劑的使用量為0重量份~100重量份,優選為0.02重量份~60重量份,更優選 為0.05重量份~2重量份。另外,相對於本發明的硬化性樹脂組成物100重量份,熱聚合起始劑的使用量為0重量份~50重量份,優選為0.01重量份~30重量份。 For thermal polymerization, it is preferred to formulate a radical polymerization initiator, which is only photohardened. When you are not, you can also not deploy. Preferred radical polymerization initiators are exemplified by well-known benzoyl peroxide, p-chlorobenzidine peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, peroxidation. Peroxide such as t-butyl pivalate, and 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2 , 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-(methyl isobutyrate), α,α-azobis An azo compound such as (isobutyronitrile) or 4,4'-azobis-(4-cyanovaleric acid). The amount of the thermal polymerization initiator used is from 0 part by weight to 100 parts by weight, preferably from 0.02 part by weight to 60 parts by weight, more preferably 100 parts by weight to the compound of the formula (1). It is 0.05 parts by weight to 2 parts by weight. In addition, the amount of the thermal polymerization initiator used is from 0 part by weight to 50 parts by weight, preferably from 0.01 part by weight to 30 parts by weight, per 100 parts by weight of the curable resin composition of the present invention.
通過使本發明的樹脂組成物硬化,而可以獲得本發明的硬化物。 為了提高所述硬化物的密接性、硬度、耐鹼性、平坦性等特性,可以在含有所述通式(3)的酸酐加成物的樹脂組成物中,根據需要調配:環氧樹脂(苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、三苯酚甲烷系環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂等)、或這些環氧樹脂與(甲基)丙烯酸反應而得的環氧(甲基)丙烯酸酯、或所述環氧(甲基)丙烯酸酯與所述酸酐反應而得的反應產物等含有高分子不飽和基的樹脂、或可以聚合的單官能及多官能(甲基)丙烯酸酯類。在含有通式(1)環氧丙烯酸酯樹脂的樹脂組成物中,根據需要也同樣可以調配。 The cured product of the present invention can be obtained by hardening the resin composition of the present invention. In order to improve characteristics such as adhesion, hardness, alkali resistance, and flatness of the cured product, a resin composition containing the acid anhydride adduct of the above formula (3) may be blended as needed: epoxy resin ( Phenolic novolac epoxy resin, cresol novolac epoxy resin, trisphenol methane epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, etc., or these epoxy resins and (methyl) An epoxy (meth) acrylate obtained by reacting acrylic acid, or a reaction product obtained by reacting the epoxy (meth) acrylate with the acid anhydride, or the like, or a polymerizable unsaturated resin. Monofunctional and polyfunctional (meth) acrylates. The resin composition containing the epoxy acrylate resin of the general formula (1) can be formulated in the same manner as needed.
多官能(甲基)丙烯酸酯類可以列舉:(甲基)丙烯酸2-羥基乙酯、 1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二丙烯酸酯、新戊二醇己二酸酯二丙烯酸酯、羥基新戊酸新戊二醇丙烯酸酯、二丙烯酸二環戊酯、己內酯改質二丙烯酸二環戊烯酯、環氧乙烷(Ethylene Oxide,EO)改質磷酸二丙烯酸酯、烯丙基化環己基二丙烯酸酯、異氰尿酸二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、丙酸改質二季戊四醇三(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷(Propylene Oxide,PO)改質三羥甲基丙烷三丙烯酸酯、三(丙烯醯氧基乙基)異氰尿酸酯、丙酸改質二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、己內酯改質二季戊四醇六丙烯酸酯、1,3-雙(3-丙烯醯氧基丙基)-1,1,3,3-四甲 基二矽氧烷、1,3-雙(3-丙烯醯氧基丙基)-1,1,3,3-四甲基二矽氧烷等。 Examples of the polyfunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate. 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalate Acid neopentyl glycol acrylate, dicyclopentanyl diacrylate, caprolactone modified dicyclopentenyl diacrylate, ethylene oxide (Ethylene Oxide, EO) modified phosphodiacrylate, allylate ring Hexyl diacrylate, isocyanuric acid diacrylate, trimethylolpropane triacrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate, pentaerythritol tri(meth)acrylate, Propylene Oxide (PO) modified trimethylolpropane triacrylate, tris(propylene decyloxyethyl)isocyanurate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , caprolactone modified dipentaerythritol hexaacrylate, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetra Dioxasiloxane, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetramethyldioxane, and the like.
此外,可以添加:無機填充劑(例如滑石、二氧化矽、氧化鋁、硫酸鋇、氧化鎂等)、或觸變劑(例如Aerosil(商品名)等)、或熱塑性彈性體、或橡膠成分(丙烯腈橡膠、腈丁二烯橡膠等)、或三聚氰胺樹脂(例如六甲氧基三聚氰胺、六丁氧基三聚氰胺等)、或勻平劑(例如矽酮、氟系聚合物、丙烯酸系共聚物等)、或矽烷偶合劑(例如含有環氧基的三甲氧基矽烷、含有巰基的三甲氧基矽烷等)、或著色顏料(例如酞菁綠、酞菁藍等)、或消泡劑、或紫外線吸收劑、或抗氧化劑、或聚合抑制劑、或勻平劑等。 Further, an inorganic filler (for example, talc, cerium oxide, aluminum oxide, barium sulfate, magnesium oxide, or the like), a thixotropic agent (for example, Aerosil (trade name), etc.), or a thermoplastic elastomer or a rubber component may be added ( An acrylonitrile rubber, a nitrile butadiene rubber, or the like, or a melamine resin (for example, hexamethoxymelamine or hexabutoxy melamine) or a leveling agent (for example, an anthrone, a fluorine-based polymer, an acrylic copolymer, etc.) Or a decane coupling agent (for example, an epoxy group-containing trimethoxy decane, a decyl group-containing trimethoxy decane, etc.), or a coloring pigment (for example, phthalocyanine green, phthalocyanine blue, etc.), or an antifoaming agent, or ultraviolet absorbing agent. Agent, or antioxidant, or polymerization inhibitor, or leveling agent, and the like.
本發明的樹脂組成物中所使用的多官能(甲基)丙烯酸酯,可以使用所述多官能(甲基)丙烯酸酯。優選列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、羥基(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基新戊酸新戊二醇(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改質二(甲基)丙烯酸二環戊烯酯、EO改質磷酸二(甲基)丙烯酸酯、烯丙基化環己基二(甲基)丙烯酸酯、異氰尿酸二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改質二季戊四醇三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、PO改質三羥甲基丙烷三(甲基)丙烯酸酯、EO改質三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧基乙基)異氰尿酸酯、丙酸改質二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯、1,3-雙(3-丙烯醯氧基丙基)-1,1,3,3-四甲基二矽氧烷、1,3-雙(3-丙烯醯氧基丙基)-1,1,3,3-四甲基 二矽氧烷等。這些多官能(甲基)丙烯酸酯會使所述光硬化或熱硬化變得更充分,是為了提高硬化物的耐化學品性、耐酸性、耐熱性、機械特性、介電常數、介電損耗角正切等而使用,可以單獨使用,也可以組合2種以上而使用。 The polyfunctional (meth) acrylate used in the resin composition of the present invention can be used as the polyfunctional (meth) acrylate. Preferably, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxy(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , neopentyl glycol adipate di(meth) acrylate, hydroxypivalic acid neopentyl glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, caprolactone modified bis ( Dicyclopentenyl methacrylate, EO modified di(meth) acrylate, allylated cyclohexyl di(meth) acrylate, isocyanuric acid di(meth) acrylate, trishydroxyl Propane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol (meth)acrylate, PO modified trimethylolpropane Tris(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, tris(propyleneoxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(methyl) Acrylate, two Pentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, 1,3-bis(3-acryloxypropyl)-1,1,3,3-tetra Dioxazane, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetramethyl Dioxane and the like. These polyfunctional (meth) acrylates make the photohardening or thermal hardening more sufficient to improve the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric constant, dielectric loss of the cured product. The angle tangent may be used alone or in combination of two or more.
相對於本發明的樹脂100重量份,在調配多官能(甲基)丙烯酸酯 時的使用量通常為5重量份~100重量份,為了進一步提高介電常數、介電損耗角正切,優選在10重量份~50重量份的範圍內進行選擇。在所述量小於5重量份時,光硬化性不充分,且無法充分地發揮出硬化物的耐化學品性、耐酸性、耐熱性、機械特性、介電性等的提高效果,或者若所述量超過100重量份,則表面硬化過好,因此在表面層產生龜裂、或難以硬化至內部。另外,相對於樹脂組成物100重量份,所述使用量通常為2.5重量份~50重量份,優選為5重量份~25重量份。 Formulating a polyfunctional (meth) acrylate with respect to 100 parts by weight of the resin of the present invention The amount to be used is usually from 5 parts by weight to 100 parts by weight, and in order to further increase the dielectric constant and the dielectric loss tangent, it is preferably selected in the range of 10 parts by weight to 50 parts by weight. When the amount is less than 5 parts by weight, the photocurability is insufficient, and the effect of improving the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric properties, etc. of the cured product cannot be sufficiently exhibited, or When the amount is more than 100 parts by weight, the surface hardening is too good, so that cracks occur in the surface layer or it is difficult to harden to the inside. Further, the amount used is usually from 2.5 parts by weight to 50 parts by weight, preferably from 5 parts by weight to 25 parts by weight, per 100 parts by weight of the resin composition.
用以製作本發明的硬化物的硬化性樹脂組成物,如上所述般需要 本發明的樹脂(通式(1)或通式(3)所示的環氧丙烯酸酯樹脂或環氧丙烯酸酯酸酐加成物),並調配光聚合起始劑等添加劑,但優選的組成物為如下所述的組成。在為包含環氧丙烯酸酯酸酐加成物的感光性樹脂組成物時,相對於本發明的樹脂100重量份,光聚合起始劑為1重量份~20重量份、優選為1重量份~5重量份,光增感劑為0.01重量份~5重量份、優選為0.5重量份~2重量份,自由基聚合起始劑為0.01重量份~30重量份、優選為0.05重量份~2重量份,3官能以上的多官能(甲基)丙烯酸酯為5重量份~50重量份、優選為10重量份~50重量份,環氧樹脂為5重量份~30重量份、優選為10重量份~20重量份,溶劑為製成所期望的黏度的量, 其他固體成分為0重量份~50重量份、優選為0重量份~20重量份。在為包含環氧丙烯酸酯樹脂或環氧丙烯酸酯酸酐加成物的熱硬化性樹脂組成物時,相對於本發明的樹脂100重量份,自由基聚合起始劑為0.01重量份~30重量份、優選為0.05重量份~2重量份,3官能以上的多官能(甲基)丙烯酸酯為5重量份~50重量份、優選為10重量份~50重量份,環氧樹脂為5重量份~30重量份、優選為10重量份~20重量份,溶劑為製成所期望的黏度的量,其他固體成分為0重量份~50重量份、優選為0重量份~20重量份。 The curable resin composition for producing the cured product of the present invention is required as described above The resin of the present invention (an epoxy acrylate resin or an epoxy acrylate anhydride adduct represented by the formula (1) or (3)), and an additive such as a photopolymerization initiator, but a preferred composition It is a composition as described below. In the case of a photosensitive resin composition containing an epoxy acrylate anhydride addition product, the photopolymerization initiator is 1 part by weight to 20 parts by weight, preferably 1 part by weight to 5 parts by weight based on 100 parts by weight of the resin of the present invention. The light sensitizer is 0.01 parts by weight to 5 parts by weight, preferably 0.5 parts by weight to 2 parts by weight, and the radical polymerization initiator is 0.01 parts by weight to 30 parts by weight, preferably 0.05 parts by weight to 2 parts by weight. The trifunctional or higher polyfunctional (meth) acrylate is 5 parts by weight to 50 parts by weight, preferably 10 parts by weight to 50 parts by weight, and the epoxy resin is 5 parts by weight to 30 parts by weight, preferably 10 parts by weight. 20 parts by weight, the solvent is the amount of the desired viscosity, The other solid content is from 0 part by weight to 50 parts by weight, preferably from 0 part by weight to 20 parts by weight. In the case of a thermosetting resin composition containing an epoxy acrylate resin or an epoxy acrylate anhydride adduct, the radical polymerization initiator is 0.01 to 30 parts by weight based on 100 parts by weight of the resin of the present invention. Preferably, it is 0.05 parts by weight to 2 parts by weight, and the trifunctional or higher polyfunctional (meth) acrylate is 5 parts by weight to 50 parts by weight, preferably 10 parts by weight to 50 parts by weight, and the epoxy resin is 5 parts by weight. 30 parts by weight, preferably 10 parts by weight to 20 parts by weight, the solvent is an amount to obtain a desired viscosity, and the other solid content is 0 parts by weight to 50 parts by weight, preferably 0 parts by weight to 20 parts by weight.
此處,本發明的樹脂在固體成分中所占的比例優選為50重量%以上。另外,在樹脂組成物中調配環氧丙烯酸酯、多官能丙烯酸酯等時,在其為通式(1)所示的化合物時,作為通式(1)所示的化合物進行計算。 Here, the proportion of the resin of the present invention in the solid content is preferably 50% by weight or more. Further, when an epoxy acrylate, a polyfunctional acrylate or the like is blended in the resin composition, when it is a compound represented by the formula (1), it is calculated as a compound represented by the formula (1).
為了獲得可以利用稀鹼水溶液實現顯影、且利用光進行圖案化的硬化膜,而使用具有多元酸基作為通式(3)中的X的鹼顯影型感光性樹脂組成物。通式(3)中,X中的多元酸基的比例為10%~100%、優選為50%~100%的範圍。若多元酸的殘基的比例小於10%,則未曝光部難以溶解於鹼水溶液。 In order to obtain a cured film which can be developed by a dilute aqueous alkali solution and patterned by light, an alkali-developable photosensitive resin composition having a polybasic acid group as X in the general formula (3) is used. In the general formula (3), the proportion of the polybasic acid group in X is from 10% to 100%, preferably from 50% to 100%. When the ratio of the residue of the polybasic acid is less than 10%, the unexposed portion is hardly dissolved in the aqueous alkali solution.
本發明的樹脂組成物中,優選的成分列舉:在120℃~160℃的整個範圍中,將硬化時間設為1小時之時,顯示80%~95%的硬化率的成分。在此種情況下,可以含有光或熱聚合起始劑作為必須的成分。 In the resin composition of the present invention, a preferred component is a component exhibiting a curing ratio of 80% to 95% when the curing time is 1 hour in the entire range of 120 ° C to 160 ° C. In this case, a photo or thermal polymerization initiator may be contained as an essential component.
本發明的硬化物可以通過公知的方法而得。例如,利用網版印刷法、噴霧法、輥塗法、靜電塗裝法、旋塗法、淋幕式塗佈法,在印刷基板上以5μm~100μm的膜厚塗佈樹脂組成物,將塗膜在室溫~140℃下進行 加熱時間為1分鐘~120分鐘的乾燥,優選在60℃~120℃下進行加熱時間為5分鐘~60分鐘的乾燥,接著利用紫外線照射或加熱而獲得硬化物。熱硬化條件通常為100℃~270℃、優選為160℃~250℃下,加熱時間為30分鐘~2小時。 The cured product of the present invention can be obtained by a known method. For example, a resin composition is applied on a printed substrate by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a spin coating method, or a curtain coating method at a film thickness of 5 μm to 100 μm. The film is processed at room temperature ~140 ° C The heating time is from 1 minute to 120 minutes, and drying is preferably carried out at 60 to 120 ° C for 5 minutes to 60 minutes, followed by ultraviolet irradiation or heating to obtain a cured product. The heat curing condition is usually from 100 ° C to 270 ° C, preferably from 160 ° C to 250 ° C, and the heating time is from 30 minutes to 2 hours.
在樹脂組成物為鹼顯影型感光性樹脂組成物時,利用所述方法進 行塗佈乾燥後,使光罩與塗膜直接接觸,接著照射紫外線進行曝光、硬化,接著利用0.1重量%~2重量%碳酸鈉水溶液、0.1重量%~2重量%二乙醇胺、0.1重量%~2重量%四甲基氫氧化銨水溶液等鹼水溶液,將塗膜的未照射部分溶解除去。接著將其在100℃~270℃、優選為160℃~250℃下進行加熱時間為30分鐘~2小時的熱硬化,從而獲得硬化物。 When the resin composition is an alkali-developable photosensitive resin composition, the method is used After coating and drying, the photomask and the coating film are directly contacted, and then exposed to ultraviolet light for exposure and hardening, followed by 0.1% by weight to 2% by weight of aqueous sodium carbonate solution, 0.1% by weight to 2% by weight of diethanolamine, and 0.1% by weight. An alkali aqueous solution such as a 2% by weight aqueous solution of tetramethylammonium hydroxide is used to dissolve and remove the unirradiated portion of the coating film. Next, it is subjected to thermal hardening at a temperature of from 100 ° C to 270 ° C, preferably from 160 ° C to 250 ° C, for 30 minutes to 2 hours to obtain a cured product.
[實施例] [Examples]
以下,利用實施例對本發明進行更具體地說明。 Hereinafter, the present invention will be more specifically described by way of examples.
(1)凝膠滲透層析法(GPC)測定 (1) Gel permeation chromatography (GPC) determination
使用串列地具備東曹(Tosoh)股份有限公司製造的TSKgelG4000HXL、TSKgelG3000HXL、TSKgelG2000HXL(商品名)的儀器,管柱溫度設為40℃。另外,溶離液是使用四氫呋喃,並設為1ml/min的流速,檢測器是使用RI(示差折射計)檢測器。將樣品0.1g溶解於10ml的四氫呋喃(Tetrahydrofuran,THF)中。通過利用標準聚苯乙烯的校準曲線,求出重量平均分子量(Mw)及數量平均分子量(Mn)。 An instrument equipped with TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL (trade name) manufactured by Tosoh Corporation was used in series, and the column temperature was set to 40 °C. Further, the elution solution was tetrahydrofuran and set to a flow rate of 1 ml/min, and the detector was an RI (differential refractometer) detector. 0.1 g of the sample was dissolved in 10 ml of tetrahydrofuran (THF). The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by using a calibration curve of standard polystyrene.
(2)軟化點 (2) Softening point
使用自動軟化點裝置(明峰公司製造、ASP-M4SP(商品名)),根據日本工業標準(JIS)-K-2207利用環球法進行測定。 The measurement was carried out by a ring and ball method using an automatic softening point device (manufactured by Mingfeng Co., Ltd., ASP-M4SP (trade name)) according to Japanese Industrial Standard (JIS)-K-2207.
(3)黏度 (3) Viscosity
使用博勒飛(BROOKFIELD)製造的E型旋轉黏度計(商品名)進行 測定。 E-type rotational viscometer (trade name) manufactured by BROOKFIELD Determination.
(4)環氧當量的測定 (4) Determination of epoxy equivalent
使用電位差滴定裝置,使用甲基乙基酮作為溶劑,添加溴化四乙基銨乙酸溶液,使用0.1mol/L的過氯酸-乙酸溶液進行測定。 Using a potentiometric titration apparatus, methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and the measurement was carried out using a 0.1 mol/L perchloric acid-acetic acid solution.
(5)酸值的測定 (5) Determination of acid value
使用電位差滴定裝置,使用二噁烷作為溶劑,並使用0.1N-KOH甲醇溶液進行測定。 The measurement was carried out using a potentiometric titration apparatus using dioxane as a solvent and using a 0.1 N-KOH methanol solution.
(多價羥基樹脂的合成) (Synthesis of polyvalent hydroxy resin)
合成例1 Synthesis Example 1
在1L的4口燒瓶中,投入作為多價羥基化合物成分的苯酚酚醛清漆(昭和電工製造;BRG-555(商品名)、羥基當量為105g/eq.、軟化點為67℃、150℃下的熔融黏度為0.08Pa.s)105g、作為酸催化劑的對甲苯磺酸0.055g(300ppm),並升溫至120℃。接著,在120℃下一邊攪拌一邊歷時3小時滴加苯乙烯73g(0.7莫耳)使其反應。接著,在120℃下反應1小時後,獲得苯乙烯改質多價羥基樹脂170g(StPN(苯乙烯改質的苯酚酚醛清漆樹脂))。所示羥基當量為178g/eq.、軟化點為78℃、150℃下的熔融黏度為0.13Pa.s。 A phenol novolak (manufactured by Showa Denko, BRG-555 (trade name), a hydroxyl equivalent of 105 g/eq., and a softening point of 67 ° C and 150 ° C) as a polyvalent hydroxy compound component was placed in a 1 L four-necked flask. The melt viscosity was 0.08 Pa.s), 105 g, 0.055 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 120 °C. Next, 73 g of styrene (0.7 mol) was added dropwise thereto at 120 ° C for 3 hours to cause a reaction. Next, after reacting at 120 ° C for 1 hour, 170 g of styrene-modified multivalent hydroxy resin (StPN (styrene-modified phenol novolak resin)) was obtained. The hydroxyl equivalent is 178 g/eq., the softening point is 78 ° C, and the melt viscosity at 150 ° C is 0.13 Pa. s.
合成例2 Synthesis Example 2
(環氧樹脂的合成) (synthesis of epoxy resin)
在四口可分離式燒瓶中加入合成例1中所得的StPN150g、表氯醇468g、二乙二醇二甲醚70g並攪拌溶解。在均勻地溶解後,在130mmHg的減壓下保持為65℃,歷時4小時滴加48%氫氧化鈉水溶液70.3g,在所述滴加中利用分離槽將回流餾出的水與表氯醇分離,將表氯醇返回至反應容器中,並將水排出體系外進行反應。反應結束後,將通過過濾而生成的鹽除去,接著進行水洗後將表氯醇蒸餾除去,而獲得環氧樹脂185g(StPNE(苯乙烯改質的苯酚酚醛清漆型環氧樹脂))。所得的樹脂的環氧當量為246 g/eq.、軟化點為56℃、150℃下的熔融黏度為0.10Pa.s。 To a four-neck separable flask, 150 g of StPN obtained in Synthesis Example 1, 468 g of epichlorohydrin, and 70 g of diethylene glycol dimethyl ether were added and stirred to dissolve. After uniformly dissolving, it was kept at 65 ° C under a reduced pressure of 130 mmHg, and 70.3 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. In the dropwise addition, the refluxed water and epichlorohydrin were separated by a separation tank. Separation, returning epichlorohydrin to the reaction vessel, and discharging the water out of the system for reaction. After completion of the reaction, the salt formed by filtration was removed, and then water-washing was carried out, and epichlorohydrin was distilled off to obtain 185 g of an epoxy resin (StPNE (styrene-modified phenol novolak type epoxy resin)). The resulting resin has an epoxy equivalent of 246. g/eq., softening point is 56 ° C, melt viscosity at 150 ° C is 0.10 Pa. s.
實施例1 Example 1
(環氧丙烯酸酯樹脂的合成) (Synthesis of epoxy acrylate resin)
將合成例2中所得的環氧樹脂160g溶解於卡必醇乙酸酯40g中,接著添加丙烯酸46.9g、三苯基膦3.2g、對苯二酚0.1g,在110℃下一邊吹入空氣一邊反應8小時,而獲得環氧丙烯酸酯樹脂。反應後的環氧丙烯酸酯樹脂的環氧當量為10875g/eq.、溶液的黏度為52.5Pa.s(25℃)。另外,利用0.1N-KOH/MeOH(甲醇)溶液進行滴定,結果酸值為3.2(mg-KOH/g)。將GPC圖表表示於圖1。 160 g of the epoxy resin obtained in Synthesis Example 2 was dissolved in 40 g of carbitol acetate, and then 46.9 g of acrylic acid, 3.2 g of triphenylphosphine, and 0.1 g of hydroquinone were added, and air was blown at 110 ° C. An epoxy acrylate resin was obtained while reacting for 8 hours. The epoxy equivalent of the epoxy acrylate resin after the reaction was 10875 g/eq., and the viscosity of the solution was 52.5 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH (methanol) solution gave an acid value of 3.2 (mg-KOH/g). The GPC chart is shown in Figure 1.
實施例2 Example 2
(環氧丙烯酸酯酸酐加成物的合成) (Synthesis of epoxy acrylate anhydride adduct)
在實施例1中所得的環氧丙烯酸酯樹脂中添加四氫鄰苯二甲酸酐74.2g、卡必醇乙酸酯146.6g,在110℃下反應1.5小時,而獲得環氧丙烯酸酯酸酐加成物(酸酐加成物A)。反應後的環氧丙烯酸酯酸酐加成物的環氧當量為19022g/eq.、樹脂溶液的黏度為3.5Pa.s(25℃)。另外,利用0.1N-KOH/MeOH溶液進行滴定,結果酸值為55.2(mg-KOH/g)。將GPC圖表表示於圖2。 74.2 g of tetrahydrophthalic anhydride and 146.6 g of carbitol acetate were added to the epoxy acrylate resin obtained in Example 1, and reacted at 110 ° C for 1.5 hours to obtain an epoxy acrylate anhydride addition. (Acid anhydride adduct A). The epoxy equivalent of the epoxy acrylate anhydride adduct after the reaction is 19022 g/eq., and the viscosity of the resin solution is 3.5 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 55.2 (mg-KOH/g). The GPC chart is shown in Figure 2.
參考例1 Reference example 1
(環氧丙烯酸酯樹脂的合成) (Synthesis of epoxy acrylate resin)
將苯酚酚醛清漆型環氧樹脂(新日鐵住金化學公司製造的YDPN-638(商品名)環氧當量為177g/eq.)160g溶解於卡必醇乙酸酯40g中,接著添加丙烯酸65.1g、三苯基膦3.2g、對苯二酚0.1g,在110℃下一邊吹入空氣一邊反應8小時,而獲得環氧丙烯酸酯樹脂。反應後的環氧丙烯酸酯樹脂的環氧當量為12000g/eq.、溶液的黏度為58.0Pa.s(25℃)。另外,利用0.1N-KOH/MeOH溶液進行滴定,結果酸值為2.5(mg-KOH/g)。 160 g of a phenol novolac type epoxy resin (YDPN-638 (trade name) epoxy equivalent of 177 g/eq.) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. was dissolved in 40 g of carbitol acetate, followed by addition of 65.1 g of acrylic acid. 3.2 g of triphenylphosphine and 0.1 g of hydroquinone were reacted for 8 hours while blowing air at 110 ° C to obtain an epoxy acrylate resin. The epoxy equivalent of the epoxy acrylate resin after the reaction is 12000 g/eq., and the viscosity of the solution is 58.0 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 2.5 (mg-KOH/g).
參考例2 Reference example 2
(環氧丙烯酸酯酸酐加成物的合成) (Synthesis of epoxy acrylate anhydride adduct)
在參考例1中所得的環氧丙烯酸酯樹脂中添加四氫鄰苯二甲酸酐74.2g、卡必醇乙酸酯146.6g,在110℃下反應1.5小時,而獲得環氧丙烯酸酯酸酐加成物(酸酐加成物B)。反應後的環氧丙烯酸酯酸酐加成物的環氧當量為20990g/eq.、樹脂溶液的黏度為4.0Pa.s(25℃)。另外,利用0.1N-KOH/MeOH溶液進行滴定,結果酸值為55.0(mg-KOH/g)。 74.2 g of tetrahydrophthalic anhydride and 146.6 g of carbitol acetate were added to the epoxy acrylate resin obtained in Reference Example 1, and reacted at 110 ° C for 1.5 hours to obtain an epoxy acrylate anhydride addition. (Acid anhydride adduct B). The epoxy equivalent of the epoxy acrylate anhydride adduct after the reaction is 20990 g/eq., and the viscosity of the resin solution is 4.0 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 55.0 (mg-KOH/g).
實施例3 Example 3
利用減壓蒸餾除去將實施例1中所得的環氧丙烯酸酯樹脂溶液中的卡必醇乙酸酯除去,而獲得環氧丙烯酸酯樹脂,然後,將20g所述環氧丙烯酸酯樹脂加入氟樹脂製模具中,添加二枯基過氧化物(dicumyl peroxide)0.2g,在100℃的烘箱中加熱30分鐘、在170℃下加熱1小時進行硬化。 The carbitol acetate in the epoxy acrylate resin solution obtained in Example 1 was removed by distillation under reduced pressure to obtain an epoxy acrylate resin, and then 20 g of the epoxy acrylate resin was added to the fluororesin. In the mold, 0.2 g of dicumyl peroxide was added, and the mixture was heated in an oven at 100 ° C for 30 minutes and at 170 ° C for 1 hour to be hardened.
比較例1 Comparative example 1
藉由減壓蒸餾除去將參考例1中所得的環氧丙烯酸酯樹脂溶液中的卡必醇乙酸酯除去,而獲得環氧丙烯酸酯樹脂,然後,將20g所述的環氧丙烯酸酯樹脂加入氟樹脂製模具中,添加二枯基過氧化物0.2g,在100℃的烘箱中加熱30分鐘、在170℃下加熱1小時進行硬化。 The carbitol acetate in the epoxy acrylate resin solution obtained in Reference Example 1 was removed by distillation under reduced pressure to obtain an epoxy acrylate resin, and then 20 g of the epoxy acrylate resin was added. In a mold made of a fluororesin, 0.2 g of dicumyl peroxide was added, and the mixture was heated in an oven at 100 ° C for 30 minutes and at 170 ° C for 1 hour to be cured.
將實施例3及比較例1中所得的硬化物的物性表示於表1。 The physical properties of the cured product obtained in Example 3 and Comparative Example 1 are shown in Table 1.
實施例4~實施例5及比較例2~比較例3 Example 4 to Example 5 and Comparative Example 2 to Comparative Example 3
使用實施例2中所得的環氧丙烯酸酯酸酐加成物A,使用雙酚A型環 氧樹脂(環氧樹脂A;新日鐵住金化學公司製造的YD-128(商品名)環氧當量為188g/eq.)、聯苯型環氧樹脂(環氧樹脂B;三菱化學公司製造的YX-4000H(商品名)環氧當量為195g/eq.)作為環氧樹脂成分。使用二季戊四醇六丙烯酸酯(DPHA(商品名):大賽璐氰特(Daicel-Cytec)公司製造)作為丙烯酸酯成分,使用Irgacure 907(商品名,巴斯夫(BASF)公司製造)作為光聚合起始劑,使用球狀熔融二氧化矽FB-60(商品名,電氣化學工業公司製造)作為二氧化矽成分。另外,在比較例2~比較例3中,使用參考例2中所得的酸酐加成物B。 Using the epoxy acrylate anhydride adduct A obtained in Example 2, using a bisphenol A type ring Oxygen resin (epoxy resin A; YD-128 (trade name) epoxy equivalent of 188g/eq. manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), biphenyl type epoxy resin (epoxy resin B; manufactured by Mitsubishi Chemical Corporation) YX-4000H (trade name) epoxy equivalent is 195 g/eq.) as an epoxy resin component. Dipentaerythritol hexaacrylate (DPHA (trade name): manufactured by Daicel-Cytec Co., Ltd.) was used as an acrylate component, and Irgacure 907 (trade name, manufactured by BASF) was used as a photopolymerization initiator. A spherical molten cerium oxide FB-60 (trade name, manufactured by Denki Chemical Industries, Ltd.) was used as the cerium oxide component. Further, in Comparative Example 2 to Comparative Example 3, the acid anhydride adduct B obtained in Reference Example 2 was used.
以表2所示的比例(重量份)調配所述各成分,進行輥磨機混練而製備各實施例4~實施例5及比較例2~比較例3的感光性樹脂組成物。以如下方式,對所得的各實施例4~實施例5及比較例2~比較例3的感光性樹脂組成物進行其性能評價。 The components were blended in the proportions (parts by weight) shown in Table 2, and kneaded by a roll mill to prepare photosensitive resin compositions of Examples 4 to 5 and Comparative Examples 2 to 3. The properties of the obtained photosensitive resin compositions of Examples 4 to 5 and Comparative Examples 2 to 3 were evaluated in the following manner.
關於塗膜的乾燥性、對鹼水溶液的顯影性,是在銅箔積層板上以20μm~30μm的厚度塗佈感光性樹脂組成物,使用熱風乾燥器在70℃下乾燥30分鐘,對所得的塗膜進行評價。另外,關於與基板的密接性、焊料耐熱性、硬度、耐化學品性及耐溶劑性,是使用高壓水銀燈,曝光20秒鐘的波長為365nm、照度為25mW/cm2的紫外線後,使用1重量%的碳酸鈉水溶液在25℃下進行60秒鐘顯影,然後在150℃下進行30分鐘加熱,並對完全硬化後的作為阻焊劑的塗膜進行評價。將結果表示於表2。 The drying property of the coating film and the developability to the aqueous alkali solution were such that the photosensitive resin composition was applied to a copper foil laminate in a thickness of 20 μm to 30 μm, and dried at 70 ° C for 30 minutes using a hot air dryer. The film was evaluated. In addition, regarding the adhesion to the substrate, the solder heat resistance, the hardness, the chemical resistance, and the solvent resistance, a high-pressure mercury lamp is used, and the ultraviolet light having a wavelength of 365 nm and an illuminance of 25 mW/cm 2 after exposure for 20 seconds is used. The weight % sodium carbonate aqueous solution was developed at 25 ° C for 60 seconds, then heated at 150 ° C for 30 minutes, and the completely cured coating film as a solder resist was evaluated. The results are shown in Table 2.
另外,各物性的評價基準如以下所述。 In addition, the evaluation criteria of each physical property are as follows.
(1)塗膜的乾燥性 (1) Dryness of the coating film
塗膜的乾燥性是依據JIS K-5400進行評價。評價是通過如下3個階段進行:◎:完全未發現黏性;○:發現微小的黏性;及×:發現顯著的黏性。 The drying property of the coating film was evaluated in accordance with JIS K-5400. The evaluation was carried out in the following three stages: ◎: no stickiness was found at all; ○: slight stickiness was found; and ×: significant stickiness was found.
(2)顯影性 (2) developability
使用1重量%的碳酸鈉水溶液,在25℃下進行60秒鐘顯影後,放大至40倍通過目視來評價殘存的樹脂。評價是通過如下3個階段進行:◎:在銅面上完全未殘留抗蝕劑;○:在銅面上殘留極少量的抗蝕劑;及×:在銅面上清楚地殘留抗蝕劑。 The remaining resin was evaluated by visual observation using a 1% by weight aqueous sodium carbonate solution and developing at 25 ° C for 60 seconds, and then magnifying to 40 times. The evaluation was carried out in three stages: ◎: no resist remained on the copper surface; ○: a very small amount of resist remained on the copper surface; and ×: the resist was clearly left on the copper surface.
(3)塗膜硬度 (3) Coating hardness
進行曝光、顯影後,依據JIS K-5400的試驗法,評價在145℃下加熱50分鐘的塗膜的硬度。 After exposure and development, the hardness of the coating film heated at 145 ° C for 50 minutes was evaluated in accordance with the test method of JIS K-5400.
(4)密接性 (4) Adhesion
進行曝光、顯影後,以於在145℃下加熱50分鐘的塗膜上製作至少100個栅格的方式進行交叉切割,接著,使用膠帶進行剝離試驗,通過目視來評價栅格的剝離的狀態。評價是通過如下的3個階段進行:◎:在全部的測定點處完全未發現剝離;○:在100個測定點中的1個~20個測定點處發現剝離;×:在100個測定點中的21個以上的測定點處發現剝離。 After exposure and development, cross-cut was performed so as to produce at least 100 grids on the coating film heated at 145 ° C for 50 minutes, and then a peeling test was performed using a tape, and the state of peeling of the grid was visually evaluated. The evaluation was performed in the following three stages: ◎: no peeling was observed at all the measurement points; ○: peeling was found at one to 20 measurement points among 100 measurement points; ×: at 100 measurement points Peeling was observed at 21 or more measurement points.
(5)焊料耐熱性 (5) Solder heat resistance
進行曝光、顯影後,依據JIS D-0202,將在145℃下加熱50分鐘的塗膜於260℃的焊料浴中浸漬20秒鐘,並評價浸漬後的塗膜的狀態。評價是通過如下3個階段進行:◎:塗膜的外觀無異常;○:塗膜的外觀有極少的膨脹;×:塗膜的外觀有膨脹、熔融、剝離。 After exposure and development, the coating film heated at 145 ° C for 50 minutes was immersed in a solder bath of 260 ° C for 20 seconds in accordance with JIS D-0202, and the state of the coating film after immersion was evaluated. The evaluation was carried out in three stages: ◎: the appearance of the coating film was not abnormal; ○: the appearance of the coating film was extremely small; ×: the appearance of the coating film was swollen, melted, and peeled off.
(6)耐化學品性 (6) Chemical resistance
進行曝光、顯影後,將在145℃下加熱50分鐘的塗膜分別在下述藥品中在25℃下浸漬1小時,並評價浸漬後的外觀、密接性。 After exposure and development, the coating film heated at 145 ° C for 50 minutes was immersed in the following drug at 25 ° C for 1 hour, and the appearance and adhesion after immersion were evaluated.
耐酸性:10重量%鹽酸水溶液 Acid resistance: 10% by weight aqueous hydrochloric acid solution
耐鹼性:10重量%苛性鈉水溶液 Alkali resistance: 10% by weight aqueous caustic soda solution
耐溶劑性:三氯乙烷、異丙醇 Solvent resistance: trichloroethane, isopropanol
評價是通過如下的3個階段進行:在所述耐酸性、耐鹼性、及耐溶劑性的試驗中,將均無異常設為○;將有少量膨潤設為△;及將有溶解或膨潤 設為×。 The evaluation was carried out in three stages: in the test of acid resistance, alkali resistance, and solvent resistance, no abnormality was set to ○; a small amount of swelling was set to Δ; and there was dissolution or swelling. Set to ×.
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KR20170027005A (en) * | 2015-09-01 | 2017-03-09 | 동우 화인켐 주식회사 | Photosensitive resin comopsition and cured pattern formed from the same |
JP6741163B2 (en) * | 2017-09-08 | 2020-08-19 | Dic株式会社 | Acid group-containing (meth)acrylate resin, curable resin composition, resin material for solder resist, and resist member |
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JP2695359B2 (en) * | 1992-12-17 | 1997-12-24 | 三井東圧化学株式会社 | Photosensitive resin composition and use |
JP5320130B2 (en) * | 2009-03-31 | 2013-10-23 | 新日鉄住金化学株式会社 | Polyvalent hydroxy resin, epoxy resin, production method thereof, epoxy resin composition and cured product thereof |
JP2012167142A (en) * | 2011-02-10 | 2012-09-06 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product |
-
2013
- 2013-03-21 JP JP2013058337A patent/JP2014181326A/en active Pending
-
2014
- 2014-03-14 KR KR1020140030107A patent/KR20140115988A/en not_active Application Discontinuation
- 2014-03-20 CN CN201410104392.6A patent/CN104059217A/en active Pending
- 2014-03-21 TW TW103110582A patent/TW201437245A/en unknown
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Publication number | Publication date |
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CN104059217A (en) | 2014-09-24 |
KR20140115988A (en) | 2014-10-01 |
JP2014181326A (en) | 2014-09-29 |
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