技术领域technical field
本发明涉及树脂组合物、感光性树脂组合物、树脂膜和电子装置。The present invention relates to a resin composition, a photosensitive resin composition, a resin film, and an electronic device.
背景技术Background technique
酚醛树脂由于分辨率优异、且具有高耐热性和机械强度，因此研究着在构成各种电子装置的树脂膜中的应用。Since phenolic resins are excellent in resolution, and have high heat resistance and mechanical strength, they are being studied for use in resin films constituting various electronic devices.
例如，在专利文献1中公开了能够用作IC、LSI等元件的制造中使用的超微细加工用抗蚀剂的正型光致抗蚀剂。进一步具体而言，公开了包含由间甲酚酚醛清漆树脂与邻甲酚酚醛清漆树脂构成的树脂混合物、和1,2-醌二叠氮化合物的组合物。For example, Patent Document 1 discloses a positive photoresist that can be used as a resist for ultrafine processing used in the manufacture of devices such as ICs and LSIs. More specifically, it discloses a composition including a resin mixture composed of a m-cresol novolak resin and an ortho-cresol novolak resin, and a 1,2-quinonediazide compound.
并且，根据该文献，通过采用这样的构成，能够提供一种感光度、膜残留率和与支撑体的密合性优异的正型光致抗蚀剂。And, according to this document, by employing such a configuration, it is possible to provide a positive photoresist excellent in sensitivity, film retention rate, and adhesion to a support.
并且，近年来，提出了含有使具有特定结构的酚化合物与脂肪族醛化合物缩合而得到的酚醛清漆型酚醛树脂作为必需成分的正型光致抗蚀剂组合物(例如，参考专利文献2)。In addition, in recent years, a positive photoresist composition containing, as an essential component, a novolak-type phenolic resin obtained by condensing a phenolic compound having a specific structure and an aliphatic aldehyde compound has been proposed (for example, refer to Patent Document 2). .
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本特开平2-55359号公报Patent Document 1: Japanese Patent Application Laid-Open No. 2-55359
专利文献2：日本特开2013-174702号公报Patent Document 2: Japanese Patent Laid-Open No. 2013-174702
发明内容Contents of the invention
发明要解决的技术课题The technical problem to be solved by the invention
然而，作为构成电子装置的树脂膜所需求的耐热性需要更高的水准，目前存在的包含酚醛树脂的树脂组合物无法满足该需求。However, a higher level of heat resistance is required as a resin film constituting an electronic device, and currently existing resin compositions containing a phenolic resin cannot meet this requirement.
并且，还存在这种背景，存在对于包含酚醛树脂的感光性树脂组合物的研发滞后的实际情况。Moreover, there is also such a background, and the development of a photosensitive resin composition containing a phenolic resin actually lags behind.
鉴于这种情况，本发明提供一种耐热性优异、例如在制成感光性树脂组合物时能够平衡性良好地表现优异的感光度和高耐热性的树脂组合物。In view of such circumstances, the present invention provides a resin composition that is excellent in heat resistance, for example, can express excellent sensitivity and high heat resistance in a well-balanced manner when used as a photosensitive resin composition.
用于解决技术课题的手段Means for solving technical problems
根据本发明，提供一种树脂组合物，其包含酚醛树脂和含有以下式(1)所示的重复单元的聚合物。According to the present invention, there is provided a resin composition comprising a phenol resin and a polymer containing a repeating unit represented by the following formula (1).
(式(1)中，RX、RY分别独立地为氢或碳原子数1～3的有机基团。)(In formula (1), RX andRY are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)
并且，根据本发明，提供一种包含含有下述式(1)所示的重复单元的聚合物的酸酐部位与酚醛树脂所具备的酚性羟基构成酯键的酯化合物的树脂组合物。Furthermore, according to the present invention, there is provided a resin composition including an ester compound in which an acid anhydride moiety of a polymer containing a repeating unit represented by the following formula (1) and a phenolic hydroxyl group of a phenolic resin form an ester bond.
(式(1)中，RX、RY分别独立地表示氢或碳原子数1～3的有机基团。)(In formula (1), RX and RY each independently represent hydrogen or an organic group having 1 to 3 carbon atoms.)
并且，根据本发明，提供一种包含上述树脂组合物和感光剂的感光性树脂组合物。Furthermore, according to this invention, the photosensitive resin composition containing the said resin composition and a photosensitizer is provided.
并且，根据本发明，提供一种包括上述树脂组合物的树脂膜。Furthermore, according to the present invention, there is provided a resin film including the above resin composition.
并且，根据本发明，提供一种包括上述感光性树脂组合物的树脂膜。Furthermore, according to this invention, the resin film containing the said photosensitive resin composition is provided.
并且，根据本发明，提供一种具备上述树脂膜的电子装置。Furthermore, according to the present invention, there is provided an electronic device including the above resin film.
发明效果Invention effect
根据本发明，能够提供一种耐热性优异、例如在制成感光性树脂组合物时能够平衡性良好地表现优异的感光度和耐热性的树脂组合物，以及使用了该树脂组合物的树脂膜和电子装置。According to the present invention, it is possible to provide a resin composition excellent in heat resistance, for example, capable of exhibiting excellent sensitivity and heat resistance in a well-balanced manner when made into a photosensitive resin composition, and a resin composition using the resin composition Resin films and electronic devices.
附图说明Description of drawings
上述目的、及其他目的、特征和优点通过以下阐述的优选实施方式、及其附带的以下附图进一步明确。The above object, and other objects, features, and advantages will be further clarified by the preferred embodiments described below and the accompanying drawings below.
图1是表示本实施方式的电子装置的一例的剖面图。FIG. 1 is a cross-sectional view showing an example of an electronic device according to this embodiment.
图2是实施例所使用的聚合物2和使其改质而得到的组合物的红外吸收光谱图。Fig. 2 is an infrared absorption spectrum chart of polymer 2 used in Examples and a composition obtained by modifying it.
具体实施方式Detailed ways
以下，适当使用附图对实施方式进行说明。其中，在所有附图中，对同样的构成要件标注相同的符号，适当省略说明。并且，若无特别说明，“～”表示以上至以下。Hereinafter, embodiment will be described using drawings as appropriate. However, in all the drawings, the same reference numerals are used to denote the same components, and explanations thereof are appropriately omitted. In addition, unless otherwise specified, "˜" means from above to below.
[树脂组合物][resin composition]
首先，对本实施方式的树脂组合物进行说明。First, the resin composition of the present embodiment will be described.
本实施方式的树脂组合物如下所示。The resin composition of this embodiment is as follows.
一种树脂组合物，其包含酚醛树脂和含有以下式(1)所示的重复单元的聚合物。A resin composition comprising a phenolic resin and a polymer comprising a repeating unit represented by the following formula (1).
(式(1)中，RX、RY分别独立地为氢或碳原子数1～3的有机基团。)(In formula (1), RX andRY are each independently hydrogen or an organic group having 1 to 3 carbon atoms.)
本实施方式的树脂组合物与目前存在的包含酚醛树脂的树脂组合物相比，能够表现出更高的耐热性。The resin composition of the present embodiment can express higher heat resistance than conventional resin compositions containing phenolic resins.
虽然详细的机理尚不明确，但例如可以认为如下：虽然包含酚醛树脂和含有上述式(1)所示的重复单元的聚合物，但酚醛树脂所具备的酚性羟基与式(1)所示的结构单元相作用，结果，聚合物与酚醛树脂形成紧密的连结结构。Although the detailed mechanism is not clear, for example, it can be considered as follows: Although a polymer containing a phenolic resin and a repeating unit represented by the above formula (1) is included, the phenolic hydroxyl group possessed by the phenolic resin is the same as that represented by the formula (1). The structural units interact with each other, and as a result, the polymer and the phenolic resin form a tightly linked structure.
这种本实施方式的树脂组合物适合用于感光性树脂组合物。该感光性树脂组合物可以包含树脂组合物和感光剂。Such a resin composition of this embodiment is suitably used for a photosensitive resin composition. The photosensitive resin composition may contain a resin composition and a photosensitizer.
以下，对构成本实施方式的树脂组合物的各成分进行说明。Hereinafter, each component which comprises the resin composition of this embodiment is demonstrated.
(酚醛树脂)(Phenolic Resin)
首先，对本实施方式的树脂组合物所包含的酚醛树脂进行说明。First, the phenolic resin contained in the resin composition of this embodiment is demonstrated.
本实施方式的酚醛树脂能够使用现有公知的酚醛树脂。作为上述酚醛树脂，并无特别限定，例如可列举酚醛清漆型酚醛树脂、甲阶型酚醛树脂、芳基亚烷基型酚醛树脂等。作为酚醛树脂，可以单独使用它们中的1种，也可以将具有不同重均分子量的2种以上并用，还可以将1种或2种以上与它们的预聚物并用。其中，优选使用酚醛清漆型酚醛树脂。As the phenolic resin of the present embodiment, conventionally known phenolic resins can be used. It does not specifically limit as said phenolic resin, For example, a novolak type phenolic resin, a resole type phenolic resin, an aryl alkylene type phenolic resin, etc. are mentioned. As the phenolic resin, one of these may be used alone, two or more having different weight average molecular weights may be used in combination, and one or more of these may be used in combination with a prepolymer thereof. Among these, novolak-type phenolic resins are preferably used.
酚醛清漆型酚醛树脂只要是使酚类与醛类在无催化剂或酸性催化剂的存在下进行反应而获得的树脂即可，能够根据用途适当选择。例如，还能够使用无规酚醛清漆型或高邻位酚醛清漆型的酚醛树脂。The novolak-type phenolic resin may be appropriately selected according to the application as long as it is obtained by reacting phenols and aldehydes in the absence of a catalyst or in the presence of an acidic catalyst. For example, a random novolak type or a high ortho novolak type phenolic resin can also be used.
其中，该酚醛清漆型酚醛树脂通常通过在醛类相对于酚类的摩尔比(醛类/酚类)控制在0.5～1.0的基础上进行反应而获得。Among them, the novolak-type phenolic resin is usually obtained by controlling the molar ratio of aldehydes to phenols (aldehydes/phenols) to be 0.5 to 1.0.
作为制备该酚醛清漆型酚醛树脂时所使用的酚类的具体例，例如可列举苯酚、邻甲酚、间甲酚、对甲酚、二甲苯酚、烷基酚类、邻苯二酚、间苯二酚等。并且，该些酚类可单独使用或将2种以上混合使用。Specific examples of the phenols used in the preparation of the novolak-type phenolic resin include, for example, phenol, o-cresol, m-cresol, p-cresol, xylenol, alkylphenols, catechol, m-cresol, Hydroquinone, etc. And these phenols can be used individually or in mixture of 2 or more types.
另外，作为制备酚醛清漆型酚醛树脂时所使用的醛类，例如能够使用：甲醛、多聚甲醛、苯甲醛等醛化合物；作为这些醛化合物的产生源的物质；或这些醛化合物的溶液等。其中，这些醛类可单独使用或将2种以上混合使用。In addition, as aldehydes used in the preparation of novolak-type phenolic resins, for example, aldehyde compounds such as formaldehyde, paraformaldehyde, and benzaldehyde; substances that are sources of these aldehyde compounds; or solutions of these aldehyde compounds can be used. However, these aldehydes can be used individually or in mixture of 2 or more types.
作为本实施方式的酚醛树脂的分子量，例如以重均分子量(Mw)计优选为300以上，更优选为1000以上，进一步优选为2000以上，特别优选为3000以上。通过重均分子量(Mw)为上述下限值以上，能够使树脂组合物和由树脂组合物得到的树脂膜的机械强度和耐热性提高。The molecular weight of the phenolic resin according to the present embodiment is, for example, preferably 300 or more, more preferably 1000 or more, still more preferably 2000 or more, particularly preferably 3000 or more in weight average molecular weight (Mw). The mechanical strength and heat resistance of the resin composition and the resin film obtained from a resin composition can be improved that a weight average molecular weight (Mw) is more than the said lower limit.
作为该酚醛树脂的分子量，例如以重均分子量(Mw)计优选为20000以下，更优选为18000以下，进一步优选为15000以下。通过重均分子量(Mw)为上述上限值以下，能够实现制造树脂组合物时的操作性的提高、由树脂组合物得到树脂膜时的成型性的提高。The molecular weight of the phenolic resin is, for example, preferably 20,000 or less, more preferably 18,000 or less, and still more preferably 15,000 or less in weight average molecular weight (Mw). When a weight average molecular weight (Mw) is below the said upper limit, the workability improvement at the time of manufacturing a resin composition, and the improvement of the moldability at the time of obtaining a resin film from a resin composition can be aimed at.
并且，能够实现树脂组合物和由树脂组合物得到的树脂膜的感光度的提高以及不溶解成分的析出量减少。In addition, it is possible to improve the sensitivity of the resin composition and the resin film obtained from the resin composition, and to reduce the precipitation of insoluble components.
并且，该重均分子量能够与下述聚合物同样地通过凝胶渗透色谱仪(GPC)基于使用聚苯乙烯标准物质作成的校准曲线而算出。In addition, the weight average molecular weight can be calculated by gel permeation chromatography (GPC) based on a calibration curve prepared using polystyrene standard substances similarly to the polymers described below.
(聚合物)(polymer)
本实施方式的聚合物含有上述式(1)所示的重复单元。即，本实施方式的聚合物是含有源自分子内具有环状结构的不饱和羧酸酐的单元的聚合物，例如为不饱和羧酸酐与其他单体的共聚物。在本实施方式中，分子内具有环状结构的不饱和羧酸酐可选自马来酸酐、柠康酸酐、二甲基马来酸酐或它们的衍生物，还可以选自马来酸酐、柠康酸酐、二甲基马来酸酐。它们可以单独使用，也可以将2种以上组合使用。The polymer of this embodiment contains the repeating unit represented by said formula (1). That is, the polymer of the present embodiment is a polymer containing a unit derived from an unsaturated carboxylic anhydride having a ring structure in the molecule, for example, a copolymer of an unsaturated carboxylic anhydride and another monomer. In this embodiment, the unsaturated carboxylic acid anhydride having a ring structure in the molecule can be selected from maleic anhydride, citraconic anhydride, dimethyl maleic anhydride or their derivatives, and can also be selected from maleic anhydride, citraconic anhydride anhydride, dimethylmaleic anhydride. These may be used individually or in combination of 2 or more types.
作为本实施方式的聚合物所具有的源自分子内具有环状结构的不饱和羧酸酐的单元，例如能够使用下述式(1)所示的源自分子内具有环状结构的不饱和羧酸酐的单元，还能够使用下述式(6)所示的源自马来酸酐的单元。As the unit derived from an unsaturated carboxylic acid anhydride having a cyclic structure in the molecule contained in the polymer of the present embodiment, for example, a unit derived from an unsaturated carboxylic acid anhydride having a cyclic structure in the molecule represented by the following formula (1) can be used. As the acid anhydride unit, a unit derived from maleic anhydride represented by the following formula (6) can also be used.
(式(1)中，RX、RY分别独立地为氢或碳原子数1～3的有机基团)(In formula (1), RX andRY are each independently hydrogen or an organic group with 1 to 3 carbon atoms)
在本实施方式中，上述式(1)中，RX和RY例如优选分别独立地为氢或碳原子数1～3的有机基团，更优选分别独立地为氢或碳原子数1的有机基团，进一步优选RX为氢、且RY为氢或碳原子数1的有机基团，更进一步优选RX和RY为氢。In the present embodiment, in the above-mentioned formula (1), RX andRY are, for example, preferably independently hydrogen or an organic group having 1 to 3 carbon atoms, and more preferably independently hydrogen or an organic group having 1 carbon atom. As for the organic group, it is more preferable that RX is hydrogen, andRY is hydrogen or an organic group having 1 carbon atoms, and it is still more preferable that RX andRY are hydrogen.
在本实施方式中，上述式(1)中，作为构成RX和RY的有机基团，例如可列举烷基、烯基、炔基、次烷基、环烷基和杂环基。In the present embodiment, in the above-mentioned formula (1), examples of organic groups constituting RX andRY include alkyl, alkenyl, alkynyl, alkylene, cycloalkyl, and heterocyclic groups.
作为烷基，例如可列举甲基、乙基、正丙基。作为烯基，例如可列举烯丙基和乙烯基。作为炔基，可列举乙炔基。作为次烷基，例如可列举次甲基和次乙基。作为环烷基，例如可列举环丙基。作为杂环基，例如可列举环氧基和氧杂环丁基。As an alkyl group, a methyl group, an ethyl group, and n-propyl group are mentioned, for example. As an alkenyl group, an allyl group and a vinyl group are mentioned, for example. As an alkynyl group, an ethynyl group is mentioned. As an alkylene group, a methine group and an ethylidene group are mentioned, for example. As a cycloalkyl group, a cyclopropyl group is mentioned, for example. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.
与该分子内具有环状结构的不饱和羧酸酐共聚的其他单体能够根据应用树脂组合物的用途而适当选择。Other monomers to be copolymerized with the unsaturated carboxylic acid anhydride having a cyclic structure in the molecule can be appropriately selected according to the application of the applied resin composition.
作为更具体的例子，可列举：降冰片烯、降冰片二烯、二环[2.2.1]-庚-2-烯(惯用名：2-降冰片烯)、5-甲基-2-降冰片烯、5-乙基-2-降冰片烯、5-丁基-2-降冰片烯、5-己基-2-降冰片烯、5-癸基-2-降冰片烯、5-烯丙基-2-降冰片烯、5-(2-丙烯基)-2-降冰片烯、5-(1-甲基-4-戊烯基)-2-降冰片烯、5-乙炔基-2-降冰片烯、5-苄基-2-降冰片烯、5-苯乙基-2-降冰片烯等降冰片烯类单体；茚、2-甲基茚、3-甲基茚等茚类单体；1,5,9-环十二碳三烯、顺-反-反-1,5,9-环十二碳三烯、反-反-反-1,5,9-环十二碳三烯、反-顺-顺-1,5,9-环十二碳三烯、顺-顺-顺-1,5,9-环十二碳三烯等脂环类单体；苯乙烯、乙烯基甲苯、α-甲基苯乙烯等苯乙烯类单体；氯乙烯、偏氯乙烯等乙烯类单体；全氟乙烯、全氟丙烯、偏氟乙烯等含氟乙烯类单体；乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷等含硅乙烯类单体；丙烯腈、甲基丙烯腈等含腈基的乙烯类单体；丙烯酰胺、甲基丙烯酰胺等含酰胺基的乙烯类单体；乙酸乙烯酯、丙酸乙烯酯、新戊酸乙烯酯、苯甲酸乙烯酯、桂皮酸乙烯酯等乙烯酯类；乙烯、丙烯等烯烃类；丁二烯、异戊二烯等共轭二烯类；烯丙基氯、烯丙醇等烯丙基类单体；马来酰亚胺、N-甲基马来酰亚胺、N-乙基马来酰亚胺、N-丙基马来酰亚胺、N-异丙基马来酰亚胺、N-丁基马来酰亚胺、N-异丁基马来酰亚胺、N-叔丁基马来酰亚胺等N-烷基马来酰亚胺；N-环己基马来酰亚胺、N-环戊基马来酰亚胺、N-降冰片基马来酰亚胺、N-环己基甲基马来酰亚胺、N-环戊基甲基马来酰亚胺等N-环烷基马来酰亚胺；N-苯基马来酰亚胺、N-氯苯基马来酰亚胺、N-甲基苯基马来酰亚胺、N-萘基马来酰亚胺、N-羟基苯基马来酰亚胺、N-甲氧基苯基马来酰亚胺、N-羧基苯基马来酰亚胺、N-硝基苯基马来酰亚胺等N-芳基马来酰亚胺；除N-烷基马来酰亚胺、N-环烷基马来酰亚胺、N-芳基马来酰亚胺以外，还可列举N-羟基马来酰亚胺等的马来酰亚胺类单体等。它们可单独使用1种，还可将不同的2种以上并用。As more specific examples, norbornene, norbornadiene, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, Bornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl Base-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2 -norbornene-based monomers such as norbornene, 5-benzyl-2-norbornene, 5-phenylethyl-2-norbornene; indene, 2-methylindene, 3-methylindene, etc. Monomers; 1,5,9-cyclododecatriene, cis-trans-trans-1,5,9-cyclododecatriene, trans-trans-trans-1,5,9-cyclodecatriene Dicarbatriene, trans-cis-cis-1,5,9-cyclododecatriene, cis-cis-cis-1,5,9-cyclododecatriene and other alicyclic monomers; benzene Styrene monomers such as ethylene, vinyltoluene, and α-methylstyrene; vinyl monomers such as vinyl chloride and vinylidene chloride; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; Silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; amide groups such as acrylamide and methacrylamide Vinyl monomers; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and other vinyl esters; ethylene, propylene and other olefins; butadiene, isoprene and other conjugated dienes; allyl monomers such as allyl chloride and allyl alcohol; maleimide, N-methylmaleimide, N-ethylmaleimide, N -Propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide Amines and other N-alkylmaleimides; N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-norbornylmaleimide, N-cyclohexylmethyl Maleimide, N-cyclopentylmethylmaleimide and other N-cycloalkylmaleimides; N-phenylmaleimide, N-chlorophenylmaleimide , N-methylphenylmaleimide, N-naphthylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxy N-arylmaleimides such as phenylmaleimide and N-nitrophenylmaleimide; except N-alkylmaleimide and N-cycloalkylmaleimide In addition to amines and N-arylmaleimides, maleimide-based monomers such as N-hydroxymaleimide and the like can be exemplified. These may be used individually by 1 type, and may use together different 2 or more types.
作为上述其他单体，优选使用脂环类单体中的降冰片烯型单体、苯乙烯类单体、茚类单体、马来酰亚胺类单体。即，本实施方式的聚合物优选还含有选自式(2)所示的源自降冰片烯型单体的单元、式(3)所示的源自苯乙烯类单体的单元、式(7)所示的源自茚类单体的单元和式(8)所示的源自马来酰亚胺类单体的单元中的至少一种单元。它们可单独含有1种，还可以含有不同的2种以上的单元。Among the alicyclic monomers, norbornene-based monomers, styrene-based monomers, indene-based monomers, and maleimide-based monomers are preferably used as the above-mentioned other monomers. That is, the polymer of the present embodiment preferably further contains a unit derived from a norbornene-type monomer represented by formula (2), a unit derived from a styrene-based monomer represented by formula (3), and a unit selected from the formula ( At least one unit of the indene-based monomer-derived unit represented by 7) and the maleimide-based monomer-derived unit represented by formula (8). These may contain 1 type individually, and may contain 2 or more types of different units.
通过聚合物含有这些单元，能够使本实施方式的树脂组合物和由树脂组合物得到的树脂膜的耐热性提高。When a polymer contains these units, the heat resistance of the resin composition of this embodiment and the resin film obtained from a resin composition can be improved.
(式(2)中，R1、R2、R3和R4分别独立地为氢或碳原子数1～30的有机基团；n为0、1或2。)(In formula (2), R1 , R2 , R3 and R4 are each independently hydrogen or an organic group with 1 to 30 carbon atoms; n is 0, 1 or 2.)
(式(3)中，Ra分别独立地为碳原子数1～30的有机基团；m为0以上5以下的整数。)(In formula (3), Ra are each independently an organic group having 1 to 30 carbon atoms; m is an integer of 0 to 5.)
(式(7)中，R5至R11分别独立地为氢或碳原子数1～3的有机基团。)(In formula (7), R5 to R11 are each independently hydrogen or an organic group with 1 to 3 carbon atoms.)
(式(8)中，R12独立地为氢或碳原子数1～10的有机基团。)(In formula (8), R12 is independently hydrogen or an organic group having 1 to 10 carbon atoms.)
在本实施方式中，上述式(2)中，R1～R4例如分别独立地为氢或碳原子数1～30的有机基团，优选分别独立地为氢或碳原子数1～10的有机基团，更优选分别独立地为氢或碳原子数1～3的有机基团，进一步优选分别独立地为氢或碳原子数1的有机基团。并且，上述式(2)中，n例如为0、1或2，优选为0或1，更优选为0。In the present embodiment, in the above-mentioned formula (2), R1 to R4 are, for example, independently hydrogen or an organic group having 1 to 30 carbon atoms, preferably independently hydrogen or an organic group having 1 to 10 carbon atoms. The organic groups are more preferably independently hydrogen or an organic group having 1 to 3 carbon atoms, and still more preferably independently hydrogen or an organic group having 1 carbon atom. In addition, in the above formula (2), n is, for example, 0, 1 or 2, preferably 0 or 1, and more preferably 0.
在本实施方式中，上述式(3)中，Ra例如分别独立地为氢或碳原子数1～30的有机基团，优选分别独立地为氢或碳原子数1～10的有机基团，更优选分别独立地为氢或碳原子数1～3的有机基团，进一步优选分别独立地为氢或碳原子数1的有机基团。并且，上述式(3)中，m例如为0以上5以下的整数，优选为0以上3以下的整数，更优选为0以上1以下的整数。In the present embodiment, in the above-mentioned formula (3), Ra is, for example, independently hydrogen or an organic group having 1 to 30 carbon atoms, preferably independently hydrogen or an organic group having 1 to 10 carbon atoms, More preferably, they are independently hydrogen or an organic group having 1 to 3 carbon atoms, and even more preferably they are independently hydrogen or an organic group having 1 carbon atom. In addition, in the above formula (3), m is, for example, an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably an integer of 0 to 1.
在本实施方式中，上述式(7)中，R5～R11例如分别独立地为氢或碳原子数1～3的有机基团，优选分别独立地为氢或碳原子数1的有机基团，进一步优选分别独立地为氢。In the present embodiment, in the above formula (7), R5 to R11 are, for example, independently hydrogen or an organic group with 1 to 3 carbon atoms, preferably hydrogen or an organic group with 1 carbon atom. group, more preferably each independently hydrogen.
在本实施方式中，上述式(8)中，R12例如独立地为氢或碳原子数1～10的有机基团，优选独立地为氢或碳原子数1～5的有机基团，更优选独立地为氢或碳原子数1～3的有机基团，进一步优选独立地为氢或碳原子数1的有机基团。In the present embodiment, in the above formula (8), R12 is, for example, independently hydrogen or an organic group with 1 to 10 carbon atoms, preferably independently hydrogen or an organic group with 1 to 5 carbon atoms, more It is preferably independently hydrogen or an organic group having 1 to 3 carbon atoms, more preferably independently hydrogen or an organic group having 1 carbon atom.
构成R1～R4、Ra的碳原子数1～30的有机基团可以在其结构中含有选自O、N、S、P和Si中的1种以上的原子。并且，构成R5～R11的碳原子数1～3的有机基团可以在其结构中含有选自O、N、S、P和Si中的1种以上的原子。并且，构成R12的碳原子数1～10的有机基团可以在其结构中含有选自O、N、S、P和Si中的1种以上的原子。并且，构成R1～R4、Ra、R5～R11和R12的有机基团均可以为不具有酸性官能团的基团。由此，能够容易地控制聚合物的酸值。The organic group having 1 to 30 carbon atoms constituting R1 to R4 and Ra may contain one or more atoms selected from O, N, S, P and Si in its structure. In addition, the organic groups having 1 to 3 carbon atoms constituting R5 to R11 may contain one or more atoms selected from O, N, S, P, and Si in their structures. In addition, the organic group having 1 to 10 carbon atoms constituting R12 may contain one or more atoms selected from the group consisting of O, N, S, P, and Si in its structure. In addition, the organic groups constituting R1 to R4 , Ra, R5 to R11 and R12 may all be groups that do not have an acidic functional group. Thereby, the acid value of a polymer can be controlled easily.
在本实施方式中，作为构成R1～R4、Ra的有机基团，例如可列举烷基、烯基、炔基、次烷基、芳基、芳烷基、烷芳基、环烷基和杂环基。In the present embodiment, examples of organic groups constituting R1 to R4 and Ra include alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, aryl groups, aralkyl groups, alkaryl groups, and cycloalkyl groups. and heterocyclyl.
作为烷基，例如可列举甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、新戊基、己基、庚基、辛基、壬基和癸基。作为烯基，例如可列举烯丙基、戊烯基和乙烯基。作为炔基，可列举乙炔基。作为次烷基，例如可列举次甲基和次乙基。作为芳基，例如可列举甲苯基、二甲苯基、苯基、萘基和蒽基。作为芳烷基，例如可列举苄基和苯乙基。作为环烷基，例如可列举金刚烷基、环戊基、环己基和环辛基。作为杂环基，例如可列举环氧基和氧杂环丁基。Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl base, nonyl and decyl. Examples of the alkenyl group include allyl, pentenyl and vinyl. As an alkynyl group, an ethynyl group is mentioned. As an alkylene group, a methine group and an ethylidene group are mentioned, for example. Examples of the aryl group include tolyl, xylyl, phenyl, naphthyl and anthracenyl. As an aralkyl group, a benzyl group and a phenethyl group are mentioned, for example. As a cycloalkyl group, an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are mentioned, for example. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.
在本实施方式中，作为构成R5～R11的有机基团，例如可列举烷基、烯基、炔基、次烷基、环烷基和杂环基。In this embodiment, examples of organic groups constituting R5 to R11 include alkyl groups, alkenyl groups, alkynyl groups, alkylene groups, cycloalkyl groups, and heterocyclic groups.
作为烷基，例如可列举甲基、乙基、正丙基。作为烯基，例如可列举烯丙基和乙烯基。作为炔基，可列举乙炔基。作为次烷基，例如可列举次甲基和亚乙基。作为环烷基，例如可列举环丙基。作为杂环基，例如可列举环氧基和氧杂环丁基。As an alkyl group, a methyl group, an ethyl group, and n-propyl group are mentioned, for example. As an alkenyl group, an allyl group and a vinyl group are mentioned, for example. As an alkynyl group, an ethynyl group is mentioned. As an alkylene group, a methine group and an ethylene group are mentioned, for example. As a cycloalkyl group, a cyclopropyl group is mentioned, for example. As a heterocyclic group, an epoxy group and an oxetanyl group are mentioned, for example.
在本实施方式中，作为构成R12的有机基团，例如可以使用氢、或上述R1～R4、Ra所例示的有机基团中的碳原子数1～10的有机基团。In this embodiment, as the organic group constituting R12 , for example, hydrogen or an organic group having 1 to 10 carbon atoms among the organic groups exemplified by R1 to R4 and Ra above can be used.
此外，构成R1～R4、Ra、R5～R11和R12的烷基、烯基、炔基、次烷基、芳基、芳烷基、烷芳基、环烷基和杂环基的1个以上的氢原子可被卤原子取代。作为卤原子，可列举氟、氯、溴和碘。其中，优选烷基的1个以上的氢原子被取代为卤原子的卤代烷基。通过使R1～R4、Ra、R5～R11、R12中的至少任一个为卤代烷基，在使用聚合物构成固化膜时能够降低该固化膜的介电常数。并且，通过形成卤代烷基醇基，不仅能够适度地调整对于碱性显影液的溶解性，而且能够提高耐热变色性。In addition, the alkyl, alkenyl, alkynyl, alkylene, aryl, aralkyl, alkaryl, cycloalkyl and heterocycle constituting R1 to R4 , Ra, R5 to R11 and R12 One or more hydrogen atoms in the group may be substituted by halogen atoms. As the halogen atom, fluorine, chlorine, bromine and iodine are exemplified. Among them, a halogenated alkyl group in which one or more hydrogen atoms of the alkyl group are substituted with halogen atoms is preferred. When at least one of R1 to R4 , Ra, R5 to R11 , and R12 is a haloalkyl group, the dielectric constant of the cured film can be reduced when the cured film is formed using a polymer. Furthermore, by forming a halogenated alkyl alcohol group, not only the solubility to an alkaline developing solution can be moderately adjusted, but also thermal discoloration resistance can be improved.
另外，从提高包含聚合物而构成的膜的透光性的观点出发，优选R1～R4、Ra、R5～R11和R12中的任一个为氢，例如在采用式(2)的结构单元的情况下，优选R1～R4均为氢。例如在采用式(3)的结构单元的情况下，优选Ra为氢。例如在采用式(7)的结构单元的情况下，优选R5～R11为氢。例如在采用式(8)的结构单元的情况下，优选R12为氢。In addition, from the viewpoint of improving the light transmittance of a film composed of a polymer, it is preferable that any one of R1 to R4 , Ra, R5 to R11 and R12 is hydrogen, for example, when formula (2) is used In the case of the structural unit, R1 to R4 are preferably all hydrogen. For example, when the structural unit of formula (3) is used, Ra is preferably hydrogen. For example, when the structural unit of formula (7) is used, R5 to R11 are preferably hydrogen. For example, when a structural unit of formula (8) is used, R12 is preferably hydrogen.
为了调节聚合物的分子量，能够适当使用链转移剂。作为链转移剂，例如可列举：3-巯基丙酸十八烷酯、季戊四醇四(3-巯基丙酸酯)、β-巯基丙酸、3-巯基丙酸甲氧基丁酯、3-巯基丙酸十八烷酯、三羟甲基丙烷三(3-巯基丙酸酯)、三-[(3-巯基丙酰氧基)-乙基]异氰脲酸酯等β-巯基丙酸类；2-羟基-1,4-萘醌、1,4-萘醌等萘醌类；正己基硫醇、正辛基硫醇、正十二烷基硫醇、叔十二烷基硫醇、巯基乙酸、巯基丙酸等硫醇类；二硫化二甲基黄原酸酯、二硫化二异丙基黄原酸酯等黄原酸类；以及三乙氧基硅烷、萜品油烯、α-甲基苯乙烯二聚物等。In order to adjust the molecular weight of the polymer, a chain transfer agent can be used appropriately. Examples of the chain transfer agent include octadecyl 3-mercaptopropionate, pentaerythritol tetrakis(3-mercaptopropionate), β-mercaptopropionic acid, methoxybutyl 3-mercaptopropionate, 3-mercapto β-mercaptopropionic acids such as octadecyl propionate, trimethylolpropane tris(3-mercaptopropionate), tris-[(3-mercaptopropionyloxy)-ethyl]isocyanurate ; 2-hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone and other naphthoquinones; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, Mercaptans such as thioglycolic acid and mercaptopropionic acid; xanthic acids such as dimethyl xanthate disulfide and diisopropyl xanthate disulfide; and triethoxysilane, terpinolene, alpha -Methylstyrene dimer, etc.
与本实施方式中的酚醛树脂进行反应之前的聚合物在利用例如GPC(凝胶渗透色谱法，Gel Permeation Chromatography)而得到的分子量分布曲线中，分子量1000以下的峰面积可以为整体的3％以下，还可以为2％以下。In the molecular weight distribution curve obtained by GPC (gel permeation chromatography, Gel Permeation Chromatography) before the polymer is reacted with the phenolic resin in this embodiment, the peak area with a molecular weight of 1000 or less may be 3% or less of the whole , can also be 2% or less.
如此，通过将利用GPC得到的分子量分布曲线的分子量1000以下的峰面积的比率设为上述范围，能够使由包含聚合物的树脂组合物构成的膜的图案形状良好。因此，能够提高具备该膜作为永久膜的液晶显示装置、固体摄像元件等电子装置的动作可靠性。Thus, by setting the ratio of the peak area of the molecular weight distribution curve obtained by GPC to molecular weight 1000 or less in the said range, the pattern shape of the film which consists of a resin composition containing a polymer can be made favorable. Therefore, the operational reliability of electronic devices such as liquid crystal display devices and solid-state imaging elements provided with this film as a permanent film can be improved.
另外，聚合物中的低分子量成分的量的下限并无特别限定。然而，本实施方式中的聚合物允许在通过GPC得到的分子量分布曲线中分子量1000以下的峰面积为整体的0.01％以上的情况。In addition, the lower limit of the amount of low molecular weight components in the polymer is not particularly limited. However, in the polymer in the present embodiment, the peak area with a molecular weight of 1000 or less in the molecular weight distribution curve obtained by GPC is allowed to be 0.01% or more of the whole.
与本实施方式中的酚醛树脂进行反应之前的聚合物例如Mw(重均分子量)/Mn(数均分子量)为1.5以上2.5以下。其中，Mw/Mn是表示分子量分布的宽度的分散度。The polymer before reacting with the phenolic resin in this embodiment, for example, Mw (weight average molecular weight)/Mn (number average molecular weight) is 1.5 or more and 2.5 or less. Here, Mw/Mn is a degree of dispersion indicating the breadth of molecular weight distribution.
本发明的发明人发现，通过将聚合物的分子量分布控制在一定的范围内，对于由该聚合物形成的膜，能够抑制固化时图案的变形。因此，通过将聚合物的Mw/Mn设为上述范围，能够使由包含聚合物的树脂组合物构成的膜的形状良好。另外，这种效果在同时如上所述地降低聚合物的低分子量成分的情况下表现得尤为显著。The inventors of the present invention found that by controlling the molecular weight distribution of a polymer within a certain range, it is possible to suppress the deformation of the pattern at the time of curing for a film formed of the polymer. Therefore, the shape of the film which consists of a resin composition containing a polymer can be made favorable by making Mw/Mn of a polymer into the said range. In addition, this effect is particularly pronounced when reducing the low-molecular-weight components of the polymer at the same time as described above.
并且，聚合物的分子量Mw(重均分子量)例如为1,500以上30,000以下。Moreover, the molecular weight Mw (weight average molecular weight) of a polymer is 1,500 or more and 30,000 or less, for example.
其中，重均分子量(Mw)、数均分子量(Mn)和分子量分布(MW/Mn)例如使用根据由GPC测定得到的标准聚苯乙烯(PS)的校准曲线求出的聚苯乙烯换算值。测定条件例如如下所示。Here, the weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MW/Mn) use, for example, polystyrene conversion values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement. Measurement conditions are, for example, as follows.
TOSOH CORPORATION生产的凝胶渗透色谱仪装置HLC-8320GPCGel permeation chromatography device HLC-8320GPC manufactured by TOSOH CORPORATION
柱：TOSOH CORPORATION生产的TSK-GEL Supermultipore HZ-MColumn: TSK-GEL Supermultipore HZ-M manufactured by TOSOH CORPORATION
检测器：液相色谱用RI检测器Detector: RI detector for liquid chromatography
测定温度：40℃Measuring temperature: 40°C
溶剂：THFSolvent: THF
试样浓度：2.0mg/毫升Sample concentration: 2.0mg/ml
另外，聚合物中的低分子量成分量例如基于由GPC测定得到的分子量相关的数据，根据相当于分子量1000以下的成分的面积总和在分子量分布整体面积中所占的比率而算出。In addition, the amount of low-molecular-weight components in the polymer is calculated from the ratio of the sum of the areas corresponding to components with a molecular weight of 1000 or less to the entire area of the molecular weight distribution based on, for example, data related to molecular weight measured by GPC.
(聚合物的制造方法)(Manufacturing method of polymer)
本实施方式的聚合物能够通过使分子内具有环状结构的不饱和羧酸酐与其他单体进行共聚而获得。该制造方法可以使用现有公知的方法。以下，列举包含上述式(2)所示的重复单元的聚合物的制造方法为例，以下进行说明。The polymer of the present embodiment can be obtained by copolymerizing an unsaturated carboxylic acid anhydride having a ring structure in the molecule with another monomer. As this production method, a conventionally known method can be used. Hereinafter, a method for producing a polymer including a repeating unit represented by the above formula (2) will be given as an example, and will be described below.
(聚合步骤(处理S1))(Aggregation step (processing S1))
首先，准备以下式(2a)所示的降冰片烯型单体与作为单体的马来酸酐。在式(2a)所示的降冰片烯型单体中，n、R1～R4可以与上述式(2)相同。First, a norbornene-type monomer represented by the following formula (2a) and maleic anhydride as a monomer are prepared. In the norbornene-type monomer represented by the formula (2a), n, R1 to R4 may be the same as those of the above-mentioned formula (2).
作为式(2a)所示的降冰片烯型单体，具体可列举二环[2.2.1]-庚-2-烯(惯用名：2-降冰片烯)。进一步作为具有烷基的降冰片烯型单体，可列举5-甲基-2-降冰片烯、5-乙基-2-降冰片烯、5-丁基-2-降冰片烯、5-己基-2-降冰片烯、5-癸基-2-降冰片烯等；作为具有烯基的降冰片烯型单体，可列举5-烯丙基-2-降冰片烯、5-(2-丙烯基)-2-降冰片烯、5-(1-甲基-4-戊烯基)-2-降冰片烯等；作为具有炔基的降冰片烯型单体，可列举5-乙炔基-2-降冰片烯等；作为具有芳烷基的降冰片烯型单体，可列举5-苄基-2-降冰片烯、5-苯乙基-2-降冰片烯等。Specific examples of the norbornene-type monomer represented by the formula (2a) include bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene). Further examples of norbornene-type monomers having an alkyl group include 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5- Hexyl-2-norbornene, 5-decyl-2-norbornene, etc.; as the norbornene type monomer having an alkenyl group, 5-allyl-2-norbornene, 5-(2 -propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, etc.; as a norbornene-type monomer having an alkynyl group, 5-acetylene group-2-norbornene, etc.; Examples of the norbornene-type monomer having an aralkyl group include 5-benzyl-2-norbornene, 5-phenylethyl-2-norbornene, and the like.
此外，作为降冰片烯型单体，能够采用在式(2a)的R1、R2、R3、R4基团的结构中包含具有交联性的基团、或含有氟等卤原子的基团等官能团的降冰片烯型单体。In addition, as norbornene-type monomers, those containing crosslinkable groups in the structure of R1 , R2 , R3 , and R4 groups in formula (2a), or those containing halogen atoms such as fluorine can be used. Norbornene-type monomers with functional groups such as groups.
作为降冰片烯型单体，能够使用它们中的任一种以上。其中，从聚合物的耐热性与透光性的平衡性的观点出发，优选使用二环[2.2.1]-庚-2-烯(惯用名：2-降冰片烯)。Any one or more of these can be used as the norbornene-type monomer. Among them, bicyclo[2.2.1]-hept-2-ene (common name: 2-norbornene) is preferably used from the viewpoint of the balance between heat resistance and light transmittance of the polymer.
接着，使式(2a)所示的降冰片烯型单体与马来酸酐进行加聚。在此，通过自由基聚合，形成式(2a)所示的降冰片烯型单体与马来酸酐的共聚物(共聚物1)。Next, the norbornene-type monomer represented by formula (2a) and maleic anhydride are subjected to polyaddition. Here, a copolymer (copolymer 1) of a norbornene-type monomer represented by formula (2a) and maleic anhydride is formed by radical polymerization.
式(2a)所示的降冰片烯型单体与马来酸酐的摩尔比(式(2a)所示的化合物的摩尔数:马来酸酐的摩尔数)优选为0.5:1～1:0.5。其中，从控制分子结构的观点出发，优选式(2a)所示的降冰片烯型单体的摩尔数:马来酸酐的摩尔数＝0.8:1～1:0.8。The molar ratio of the norbornene-type monomer represented by the formula (2a) to maleic anhydride (the number of moles of the compound represented by the formula (2a):the number of moles of maleic anhydride) is preferably 0.5:1 to 1:0.5. Among them, from the viewpoint of controlling the molecular structure, the number of moles of the norbornene-type monomer represented by the formula (2a):the number of moles of maleic anhydride=0.8:1 to 1:0.8 is preferable.
另外，在该加聚时，除上述降冰片烯型单体和马来酸酐以外，还可以添加能够进行共聚的单体。作为这种单体，可列举分子内包含具有烯属双键的基团的化合物。在此，作为具有烯属双键的基团的具体例，可列举烯丙基、丙烯酰基、甲基丙烯酰基、马来酰亚胺基或苯乙烯基或茚基等芳香族乙烯基等。In addition, in this polyaddition, a copolymerizable monomer may be added in addition to the above-mentioned norbornene-type monomer and maleic anhydride. Examples of such monomers include compounds containing a group having an ethylenic double bond in the molecule. Here, specific examples of the group having an ethylenic double bond include an allyl group, an acryloyl group, a methacryloyl group, a maleimide group, or an aromatic vinyl group such as a styryl group or an indenyl group.
另外，还可以使用其他的分子内具有环状结构的不饱和羧酸酐来代替上述马来酸酐。In addition, other unsaturated carboxylic acid anhydrides having a ring structure in the molecule may be used instead of the above-mentioned maleic anhydride.
作为聚合方法，例如优选使用自由基聚合引发剂和根据需要的链转移剂进行聚合的方法。在该情况下，能够采用悬浮聚合、溶液聚合、分散聚合、乳化聚合等方法。其中，优选溶液聚合。在溶液聚合时，可将各单体一次性添加全部量来进行，也可以将一部分添加至反应容器，再滴加剩余的单体来进行。As the polymerization method, for example, a method of performing polymerization using a radical polymerization initiator and, if necessary, a chain transfer agent is preferable. In this case, methods such as suspension polymerization, solution polymerization, dispersion polymerization, and emulsion polymerization can be employed. Among them, solution polymerization is preferable. In the case of solution polymerization, the entire amount of each monomer may be added at once, or a part may be added to the reaction vessel, and the remaining monomers may be added dropwise.
例如，通过将式(2a)所示的降冰片烯型单体、马来酸酐和聚合引发剂溶解于溶剂中，之后加热规定时间，由此使式(2a)所示的降冰片烯型单体与马来酸酐进行溶液聚合。加热温度例如为50～80℃，加热时间为10～20小时。For example, by dissolving the norbornene-type monomer represented by the formula (2a), maleic anhydride, and a polymerization initiator in a solvent, and then heating for a predetermined time, the norbornene-type monomer represented by the formula (2a) solution polymerization with maleic anhydride. The heating temperature is, for example, 50 to 80° C., and the heating time is 10 to 20 hours.
作为聚合所使用的溶剂，例如能够使用二乙醚、四氢呋喃、甲苯、甲基乙基酮、乙酸乙酯等中的任一种以上。As the solvent used for the polymerization, for example, any one or more of diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, ethyl acetate, and the like can be used.
作为自由基聚合引发剂，能够使用偶氮化合物和有机过氧化物中的任一种以上。As the radical polymerization initiator, any one or more of azo compounds and organic peroxides can be used.
作为偶氮化合物，例如可列举偶氮双异丁腈(AIBN)、2,2'-偶氮双(2-甲基丙酸)二甲酯、1,1'-偶氮双(环己烷甲腈)(ABCN)，能够使用它们中的任一种以上。Examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), 1,1'-azobis(cyclohexane Acetonitrile) (ABCN), any one or more of them can be used.
另外，作为有机过氧化物，例如可列举过氧化氢、过氧化二叔丁基(DTBP)、过氧化苯甲酰(苯甲酰过氧化物，BPO)和过氧化甲基乙基酮(MEKP)，能够使用它们中的任一种以上。In addition, examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO) and methyl ethyl ketone peroxide (MEKP). ), any one or more of them can be used.
自由基聚合引发剂的量(摩尔数)优选为式(2a)所示的降冰片烯型单体与马来酸酐的合计摩尔数的1％～10％。通过将聚合引发剂的量适当设定在上述范围内，并且适当设定反应温度、反应时间、链转移剂的量，能够将所获得的聚合物的重均分子量(Mw)调整在适当的范围。The amount (number of moles) of the radical polymerization initiator is preferably 1% to 10% of the total number of moles of the norbornene-type monomer represented by the formula (2a) and maleic anhydride. By appropriately setting the amount of the polymerization initiator within the above-mentioned range, and appropriately setting the reaction temperature, reaction time, and the amount of the chain transfer agent, the weight-average molecular weight (Mw) of the obtained polymer can be adjusted to an appropriate range. .
通过该聚合工序(处理S1)，能够将具有上述式(1)所示的重复单元和式(2)所示的重复单元的共聚物1聚合。By this polymerization step (process S1), the copolymer 1 having the repeating unit represented by the above-mentioned formula (1) and the repeating unit represented by the formula (2) can be polymerized.
其中，在共聚物1中，式(2)的结构的R1优选在各重复单元中是共通的，但也可以在各个重复单元中有所不同。在R2～R4中也同样。Among them, in the copolymer 1, R1 of the structure of the formula (2) is preferably common to each repeating unit, but may be different from each repeating unit. The same applies to R2 to R4 .
共聚物1可以是式(1)所示的重复单元与式(2)所示的重复单元无规地配置而成的结构，还可以是交替地配置而成的结构。并且，还可以是式(2a)所示的降冰片烯型单体与马来酸酐进行嵌段共聚而成的结构。其中，从确保使用本实施方式所制造的聚合物的树脂组合物的溶解性的均匀性的观点出发，优选式(1)所示的重复单元与式(2)所示的重复单元交替地配置而成的结构。即，共聚物1例如在降冰片烯型单体与马来酸酐共聚的情况下，优选为具有以下式(4)所示的重复单元的结构。Copolymer 1 may have a structure in which repeating units represented by formula (1) and repeating units represented by formula (2) are randomly arranged, or may be alternately arranged. Furthermore, a structure obtained by block copolymerizing a norbornene-type monomer represented by formula (2a) and maleic anhydride may also be used. Among them, from the viewpoint of ensuring the uniformity of solubility of the resin composition using the polymer produced in this embodiment, it is preferable that the repeating unit represented by formula (1) and the repeating unit represented by formula (2) are arranged alternately. formed structure. That is, the copolymer 1 preferably has a structure having a repeating unit represented by the following formula (4), for example, when a norbornene-type monomer and maleic anhydride are copolymerized.
(式(4)中，n、R1～R4与上述式(2)相同。即，n为0、1、2中的任一个。R1～R4为氢或碳原子数1～30的有机基团。R1～R4可以相同也可以不同。并且，a为10以上200以下的整数。)(In formula (4), n, R1 to R4 are the same as the above formula (2). That is, n is any one of 0, 1, and 2. R1 to R4 are hydrogen or carbon atoms of 1 to 30 organic group. R1 to R4 may be the same or different. In addition, a is an integer ranging from 10 to 200.)
在此，式(4)的结构的R1优选在各重复单元中是共通的，但也可以在各个重复单元中有所不同。在R2～R4中也相同。Here, R1 in the structure of formula (4) is preferably common to each repeating unit, but may be different from each repeating unit. The same applies to R2 to R4 .
(低分子量成分去除工序(处理S2))(Low molecular weight component removal step (processing S2))
接着，根据需要在包含共聚物1和残留单体及低聚物等低分子量成分的有机层中，加入大量不良溶剂，例如己烷或甲醇，使包含共聚物1的聚合物凝固沉淀。在此，作为低分子量成分，包含残留单体、低聚物以及聚合引发剂等。接着，进行过滤，使所得到的凝固物干燥。由此，可获得除去低分子量成分后的、以共聚物1为主要成分(主要生成物)的聚合物。Next, if necessary, add a large amount of poor solvent, such as hexane or methanol, to the organic layer containing copolymer 1 and low molecular weight components such as residual monomers and oligomers, to coagulate and precipitate the polymer containing copolymer 1. Here, residual monomers, oligomers, polymerization initiators, and the like are included as low molecular weight components. Next, filtration was performed to dry the obtained coagulum. Thereby, a polymer containing the copolymer 1 as a main component (main product) after removal of low molecular weight components can be obtained.
在本实施方式的树脂组合物中，聚合物的含量相对于上述酚醛树脂100质量份优选为5质量份以上，更优选为10质量份以上，进一步优选为15质量份以上，特别优选为20质量份以上。In the resin composition of the present embodiment, the content of the polymer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass with respect to 100 parts by mass of the above-mentioned phenolic resin. servings or more.
并且，在本实施方式的树脂组合物中，聚合物的含量相对于上述酚醛树脂100质量份优选为100质量份以下，更优选为70质量份以下，进一步优选为50质量份以下，特别优选为35质量份以下。In addition, in the resin composition of the present embodiment, the content of the polymer is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, particularly preferably 35 parts by mass or less.
通过设定为这样的范围，能够带来与上述酚醛树脂的适度的相互作用，更有助于提高耐热性。By setting it as such a range, moderate interaction with the said phenolic resin can be brought about, and it can contribute more to improvement of heat resistance.
例如，即便在上述聚合物包含上述式(7)所示的重复单元的情况下，还可以通过使用下述式(7a)所示的茚类单体，利用与包含式(2)的重复单元的单体和聚合物相同的方法进行制造。For example, even in the case where the above-mentioned polymer contains the repeating unit represented by the above formula (7), it is also possible to utilize the repeating unit containing the formula (2) by using an indenic monomer represented by the following formula (7a) Monomers and polymers are manufactured in the same way.
(式(7a)中，R5～R11与式(7)相同。)(In formula (7a), R5 to R11 are the same as formula (7).)
本实施方式的树脂组合物包含上述酚醛树脂和聚合物，优选包含聚合物中的式(6)所示的结构单元(即马来酸酐单元)与酚醛树脂所具备的酚性羟基经由酯键键合而成的化合物(酯化合物)。The resin composition of the present embodiment comprises the above-mentioned phenolic resin and a polymer, and preferably comprises a structural unit represented by formula (6) in the polymer (that is, a maleic anhydride unit) and a phenolic hydroxyl group possessed by the phenolic resin via an ester bond. Synthetic compounds (ester compounds).
可以认为在本实施方式的树脂组合物中，通过该酚性羟基与马来酸酐加成，提供以下式(5)所示的半酯。由于该式(5)中的酯键，本实施方式的树脂组合物、树脂膜能够表现出高耐热性。In the resin composition of this embodiment, it is considered that the half ester represented by the following formula (5) is provided by the addition of this phenolic hydroxyl group and maleic anhydride. Due to the ester bond in this formula (5), the resin composition and the resin film of the present embodiment can express high heat resistance.
并且可以认为式(5)中的半酯含有羧基，由此可实现制备感光性树脂组合物时的感光度的提高。And it is thought that the half ester in formula (5) contains a carboxyl group, and it is thought that the improvement of the sensitivity at the time of preparing a photosensitive resin composition can be aimed at by this.
另外，还可以使用其他的分子内具有环状结构的不饱和羧酸酐代替上述马来酸酐。In addition, other unsaturated carboxylic acid anhydrides having a ring structure in the molecule may be used instead of the above-mentioned maleic anhydride.
(式(5)中，R为源自酚醛树脂的原子团。)(In the formula (5), R is an atomic group derived from a phenolic resin.)
另外，可以认为本实施方式的树脂组合物如上所述提供式(5)所示的半酯。由此表现出耐热性等的效果，因此通过在供应于各种用途之前对树脂组合物进行加热等，能够增加上述半酯的含有比率。Moreover, it is thought that the resin composition of this embodiment provides the half ester represented by formula (5) as mentioned above. Thereby, effects such as heat resistance are exhibited, and therefore, the content ratio of the above-mentioned half-ester can be increased by heating the resin composition or the like before supplying it to various uses.
作为该加热的条件，例如为50～100℃的范围。The heating conditions are, for example, in the range of 50 to 100°C.
并且，例如在用于工艺中经过加热工序等的用途的情况下，还能够将上述酚醛树脂与聚合物在常温下混合使用而无需供应于加热。In addition, for example, in the case of using for an application that has undergone a heating step in the process, the above-mentioned phenolic resin and polymer can be mixed and used at normal temperature without heating.
在该加热中，从促进反应的观点出发，能够适当添加催化剂，例如能够添加碱催化剂或酸催化剂。In this heating, a catalyst can be added appropriately from the viewpoint of promoting the reaction, for example, a base catalyst or an acid catalyst can be added.
作为碱催化剂，能够使用氢氧化钠、氢氧化钾等羟基化合物，吡啶或三乙胺等烷基胺，二甲基苯胺、乌洛托品、二甲基氨基吡啶等胺化合物，乙酸钠等金属盐，氨等。它们可单独使用一种，为了进一步提高反应性，还可以将两种以上的碱催化剂组合。As the base catalyst, hydroxyl compounds such as sodium hydroxide and potassium hydroxide, alkylamines such as pyridine and triethylamine, amine compounds such as dimethylaniline, urotropine, and dimethylaminopyridine, and metals such as sodium acetate can be used. salt, ammonia, etc. One of these may be used alone, or two or more base catalysts may be combined in order to further increase reactivity.
另外，作为酸催化剂，能够使用硫酸或盐酸等无机酸、对甲苯磺酸等有机酸、氟化硼乙醚等路易斯酸等。In addition, as the acid catalyst, inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, Lewis acids such as boron fluoride diethyl ether, and the like can be used.
另外，还可以使用其他的分子内具有环状结构的不饱和羧酸酐代替上述马来酸酐。In addition, other unsaturated carboxylic acid anhydrides having a ring structure in the molecule may be used instead of the above-mentioned maleic anhydride.
并且，本实施方式的树脂组合物可以包含含有上述式(1)所示的重复单元的聚合物的酸酐部位与酚醛树脂所具备的酚性羟基构成酯键的酯化合物。在该情况下，本实施方式的树脂组合物中，该聚合物的酸酐(例如马来酸酐)可以全部开环，和/或酚醛树脂所具备的酚性羟基均可以具有酯键。由此，能够进一步提高耐热性。Furthermore, the resin composition of the present embodiment may contain an ester compound in which the acid anhydride moiety of the polymer containing the repeating unit represented by the above formula (1) forms an ester bond with the phenolic hydroxyl group of the phenolic resin. In this case, in the resin composition of the present embodiment, all acid anhydrides (for example, maleic anhydride) of the polymer may be ring-opened, and/or all phenolic hydroxyl groups of the phenolic resin may have ester bonds. Thereby, heat resistance can be further improved.
[感光性树脂组合物][Photosensitive resin composition]
作为关于上述树脂组合物的更具体的用途，能够举出如下所示的作为感光性树脂组合物的用途。As a more specific use about the said resin composition, the use as a photosensitive resin composition shown below can be mentioned.
本实施方式的感光性树脂组合物能够包含上述酚醛树脂、含有上述式(1)所示的重复单元的聚合物和感光剂。即，本实施方式的感光性树脂组合物可以包含上述树脂组合物和感光剂。The photosensitive resin composition of this embodiment can contain the said phenol resin, the polymer containing the repeating unit represented by said formula (1), and a photosensitizer. That is, the photosensitive resin composition of this embodiment may contain the above-mentioned resin composition and a photosensitizer.
在此，关于在本实施方式的感光性树脂组合物中使用的酚醛树脂和聚合物，能够采用与上述相同的物质。以下，对除这些以外的成分进行说明。Here, the same thing as above can be employ|adopted about the phenol resin and polymer used for the photosensitive resin composition of this embodiment. Hereinafter, components other than these are demonstrated.
(感光剂)(photosensitive agent)
本实施方式的感光性树脂组合物包含感光剂。The photosensitive resin composition of this embodiment contains a photosensitizer.
作为该感光剂，例如能够使用重氮醌化合物、二芳基碘鎓盐、三芳基锍盐或锍-硼酸盐等鎓盐、2-硝基苄基酯化合物、N-亚氨基磺酸盐化合物、酰亚胺磺酸盐化合物、2,6-双(三氯甲基)-1,3,5-三嗪化合物或二氢吡啶化合物。其中，特别优选使用感光度和溶剂溶解性优异的重氮醌化合物。作为重氮醌化合物，例如能够使用以下所示的化合物。As the sensitizer, for example, onium salts such as diazoquinone compounds, diaryliodonium salts, triarylsulfonium salts, or sulfonium-borates, 2-nitrobenzyl ester compounds, N-iminosulfonic acid salts, etc., can be used. compound, imidesulfonate compound, 2,6-bis(trichloromethyl)-1,3,5-triazine compound or dihydropyridine compound. Among them, it is particularly preferable to use a diazoquinone compound excellent in sensitivity and solvent solubility. As the quinone diazide compound, for example, the compounds shown below can be used.
(n2为1以上5以下的整数。)(n2 is an integer from 1 to 5.)
在以上的各化合物中，Q为下述的(a)～(c)所示的结构中的任一个或氢原子。其中，各化合物的Q中的至少一个为下述的(a)～(c)所示的结构的任一个。In each of the above compounds, Q is any one of the structures shown in (a) to (c) below or a hydrogen atom. However, at least one of Q in each compound is any one of the structures represented by the following (a)-(c).
在本实施方式中，作为重氮醌化合物，例如更优选使用酚化合物与1,2-萘醌-2-二叠氮-5-磺酸或1,2-萘醌-2-二叠氮-4-磺酸的酯。In this embodiment, as the diazide quinone compound, for example, a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide- 4-Ester of sulfonic acid.
本实施方式的感光性树脂组合物可以为所谓的正型，可以认为残留于未曝光部的凸纹图案中的感光剂因固化时的热发生分解而产生酸，该感光剂还作为反应促进剂而发挥重要作用。作为具有这样的作用的重氮醌化合物，特别优选使用更容易受热分解的1,2-萘醌-2-二叠氮-4-磺酸的酯。The photosensitive resin composition of this embodiment may be a so-called positive type, and it is considered that the photosensitive agent remaining in the relief pattern of the unexposed portion is decomposed by heat during curing to generate an acid, and the photosensitive agent also serves as a reaction accelerator. play an important role. As the diazoquinone compound having such an action, it is particularly preferable to use an ester of 1,2-naphthoquinone-2-diazide-4-sulfonic acid which is more easily decomposed by heat.
本实施方式的感光性树脂组合物中的感光剂的含量并无特别限定，相对于酚醛树脂100质量份优选为5质量份以上，更优选为8质量份以上。并且，感光性树脂组合物中的感光剂的含量相对于酚醛树脂100质量份优选为80质量份以下，更优选为60质量份以下。通过感光剂的含量在上述范围内，能够发挥良好的图案化性能。Although the content of the photosensitizer in the photosensitive resin composition of this embodiment is not specifically limited, It is preferable that it is 5 mass parts or more with respect to 100 mass parts of phenol resins, and it is more preferable that it is 8 mass parts or more. Furthermore, the content of the photosensitizer in the photosensitive resin composition is preferably 80 parts by mass or less, more preferably 60 parts by mass or less, with respect to 100 parts by mass of the phenol resin. Favorable patterning performance can be exhibited by content of a photosensitive agent being in the said range.
(溶剂)(solvent)
本实施方式所记载的树脂组合物和感光性树脂组合物能够通过将上述各成分溶解在溶剂中而以清漆状使用。The resin composition and photosensitive resin composition described in this embodiment can be used in a varnish form by dissolving each of the above-mentioned components in a solvent.
作为这种溶剂的例子，可列举N-甲基-2-吡咯啶酮、γ-丁内酯、N,N-二甲基乙酰胺、二甲基亚砜、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、丙二醇单甲醚、二丙二醇单甲醚、丙二醇单甲醚乙酸酯、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲基-1,3-丁二醇乙酸酯、1,3-丁二醇-3-单甲醚、丙酮酸甲酯、丙酮酸乙酯和甲基-3-甲氧基丙酸酯等。Examples of such solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethyl sulfoxide, diglyme, Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1 , 3-butanediol acetate, 1,3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate and methyl-3-methoxypropionate, etc.
另外，从显著抑制树脂膜产生龟裂的观点出发，在这些化合物中，优选使用选自γ-丁内酯、二甲基亚砜、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇二丁醚、丙二醇单甲醚、二丙二醇单甲醚、丙二醇单甲醚乙酸酯中的化合物。In addition, from the viewpoint of significantly suppressing the occurrence of cracks in the resin film, among these compounds, it is preferable to use a compound selected from γ-butyrolactone, dimethyl sulfoxide, diglyme, diethylene glycol diethyl ether, Compounds in Diethylene Glycol Dibutyl Ether, Propylene Glycol Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate.
本实施方式的树脂组合物和感光性树脂组合物中的溶剂的含量并无特别限定，相对于酚醛树脂100质量份，优选为100质量份以上，更优选为150质量份以上。The content of the solvent in the resin composition and photosensitive resin composition of the present embodiment is not particularly limited, but is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, based on 100 parts by mass of the phenol resin.
并且，本实施方式的树脂组合物和感光性树脂组合物中的溶剂的含量相对于酚醛树脂100质量份优选为1000质量份以下，更优选为800质量份以下。溶剂的含量在上述范围内时，能够带来适度的操作性。Furthermore, the content of the solvent in the resin composition and the photosensitive resin composition of the present embodiment is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, based on 100 parts by mass of the phenol resin. When the content of the solvent is within the above range, moderate workability can be brought about.
(其他成分)(other ingredients)
本实施方式的树脂组合物和感光性树脂组合物除了配合上述成分以外，还能够根据用途配合各种成分。The resin composition and photosensitive resin composition of this embodiment can mix|blend various components other than the above-mentioned component according to a use.
例如，作为碱可溶性树脂，可以另外配合酚醛树脂、苯酚芳烷基树脂、羟基苯乙烯树脂、甲基丙烯酸树脂、甲基丙烯酸酯树脂等丙烯酸类树脂、环状烯烃类树脂等。For example, as the alkali-soluble resin, acrylic resins such as phenol resins, phenol aralkyl resins, hydroxystyrene resins, methacrylic resins, and methacrylate resins, cyclic olefin resins, and the like can be additionally blended.
此外，还可以根据需要添加抗氧化剂、填料、硅烷偶联剂、表面活性剂、密合助剂、封端剂和敏化剂等添加物。In addition, additives such as antioxidants, fillers, silane coupling agents, surfactants, adhesion aids, blocking agents, and sensitizers may be added as needed.
另外，它们的添加量是任意的。In addition, their addition amounts are arbitrary.
(用途)(use)
本实施方式的树脂组合物和感光性树脂组合物能够用于形成抗蚀剂或永久膜等树脂膜。从耐热性的观点出发，优选这样的用途。The resin composition and photosensitive resin composition of this embodiment can be used for forming resin films, such as a resist and a permanent film. Such use is preferable from the viewpoint of heat resistance.
并且，上述抗蚀剂例如由通过利用旋涂、辊涂、流涂、浸涂、喷涂、刮涂等方法涂布感光性树脂组合物并将溶剂去除而获得的树脂膜构成。In addition, the above-mentioned resist is constituted by, for example, a resin film obtained by applying a photosensitive resin composition by methods such as spin coating, roll coating, flow coating, dip coating, spray coating, and blade coating, and removing the solvent.
上述永久膜由通过对上述树脂膜进行曝光和显影，图案化为所需形状后，利用热处理等使其固化而获得的固化膜构成。永久膜例如可用于保护膜、层间膜或缓冲材料等。The above-mentioned permanent film is composed of a cured film obtained by exposing and developing the above-mentioned resin film, patterning it into a desired shape, and then curing it by heat treatment or the like. The permanent film can be used, for example, as a protective film, an interlayer film, or a cushioning material, among others.
接着，对应用了本实施方式的树脂组合物或感光性树脂组合物的电子装置100的一例进行说明。Next, an example of the electronic device 100 to which the resin composition or the photosensitive resin composition of this embodiment is applied will be described.
本实施方式的电子装置100能够具备上述树脂膜。The electronic device 100 of the present embodiment can include the resin film described above.
图1所示的电子装置100例如为半导体芯片。在该情况下，例如通过将电子装置100经由凸块52搭载在配线基板上，得到半导体封装体。电子装置100具备设置有晶体管等半导体元件的半导体基板和在半导体基板上设置的多层配线层(未图示)。在多层配线层中的最上层设置有层间绝缘膜30及在层间绝缘膜30上设置的最上层配线34。最上层配线34例如由铝构成。并且，在层间绝缘膜30上和最上层配线34上设置有钝化膜32。在钝化膜32的一部分设置有最上层配线34露出的开口。The electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip. In this case, for example, the semiconductor package is obtained by mounting the electronic device 100 on the wiring board via the bumps 52 . The electronic device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate. An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided on the uppermost layer among the multilayer wiring layers. The uppermost wiring 34 is made of, for example, aluminum. Furthermore, a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost wiring 34 . An opening through which the uppermost layer wiring 34 is exposed is provided in a part of the passivation film 32 .
在钝化膜32上设置有再配线层40。再配线层40具有设置在钝化膜32上的绝缘层42、设置在绝缘层42上的再配线46、以及设置在绝缘层42上和再配线46上的绝缘层44。绝缘层42形成有与最上层配线34连接的开口。再配线46形成于绝缘层42上和绝缘层42所设置的开口内，与最上层配线34连接。绝缘层44设置有与再配线46连接的开口。A rewiring layer 40 is provided on the passivation film 32 . The rewiring layer 40 has an insulating layer 42 provided on the passivation film 32 , a rewiring 46 provided on the insulating layer 42 , and an insulating layer 44 provided on the insulating layer 42 and the rewiring 46 . The insulating layer 42 is formed with an opening connected to the uppermost layer wiring 34 . The rewiring 46 is formed on the insulating layer 42 and in the opening provided in the insulating layer 42 , and is connected to the uppermost layer wiring 34 . The insulating layer 44 is provided with an opening connected to the rewiring 46 .
在本实施方式中，能够由通过使上述树脂组合物或感光性树脂组合物固化而形成的树脂膜构成钝化膜32、绝缘层42和绝缘层44中的一个以上。在该情况下，例如对由感光性树脂组合物形成的涂布膜曝光紫外线并进行显影而图案化，之后，对其进行加热固化，由此形成钝化膜32、绝缘层42或绝缘层44。In this embodiment, one or more of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be comprised with the resin film formed by hardening the said resin composition or the photosensitive resin composition. In this case, the passivation film 32, the insulating layer 42, or the insulating layer 44 is formed by exposing, for example, ultraviolet rays to a coating film formed of a photosensitive resin composition, developing and patterning, and then heating and curing it. .
在绝缘层44所设置的开口内，例如隔着UBM(Under Bump Metallurgy：凸块下金属)层50形成凸块52。电子装置100例如经由凸块52与配线基板等连接。In the opening provided in the insulating layer 44 , for example, a bump 52 is formed via a UBM (Under Bump Metallurgy: Under Bump Metallurgy) layer 50 . The electronic device 100 is connected to a wiring board or the like via bumps 52 , for example.
另外，本发明并不限定于上述实施方式，能够实现本发明目的的范围内的变形、改良等包括在本发明中。In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope of achieving the object of the present invention are included in the present invention.
以下，附记参考方式的示例。Below, an example of the reference method is appended.
1.一种树脂组合物，其包含酚醛清漆型酚醛树脂和含有以下式(6)所示的重复单元的聚合物。1. A resin composition comprising a novolak-type phenolic resin and a polymer containing a repeating unit represented by the following formula (6).
2.根据1.所述的树脂组合物，其中，上述酚醛清漆型酚醛树脂的重均分子量为300以上20000以下。2. The resin composition according to 1., wherein the weight average molecular weight of the novolak-type phenolic resin is 300 to 20,000.
3.根据1.或2.所述的树脂组合物，其包含具备上述式(6)所示的重复单元的酸酐部位与上述酚醛清漆型酚醛树脂所具备的酚性羟基经由酯键键合而成的化合物。3. The resin composition according to 1. or 2., which comprises an acid anhydride moiety having a repeating unit represented by the above-mentioned formula (6) and a phenolic hydroxyl group possessed by the above-mentioned novolak-type phenolic resin via an ester bond. into compounds.
4.根据1.至3.中任一项所述的树脂组合物，其中，上述聚合物还含有以下式(2)所示的重复单元或以下式(3)所示的重复单元。4. The resin composition according to any one of 1. to 3., wherein the polymer further contains a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3).
(式(2)中，R1、R2、R3和R4分别独立地为氢或碳原子数1～30的有机基团；n为0、1或2。)(In formula (2), R1 , R2 , R3 and R4 are each independently hydrogen or an organic group with 1 to 30 carbon atoms; n is 0, 1 or 2.)
(式(3)中，Ra分别独立地为碳原子数1～30的有机基团。m为0以上5以下的整数。)(In formula (3), Ra is each independently an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 5.)
5.一种感光性树脂组合物，其包含酚醛清漆型酚醛树脂、含有以下式(6)所示的重复单元的聚合物和感光剂。5. A photosensitive resin composition comprising a novolak-type phenol resin, a polymer containing a repeating unit represented by the following formula (6), and a photosensitizer.
6.根据5.所述的感光性树脂组合物，其中，上述感光剂为重氮醌化合物。6. The photosensitive resin composition according to 5., wherein the photosensitive agent is a diazoquinone compound.
7.根据5.或6.所述的感光性树脂组合物，其中，上述酚醛清漆型酚醛树脂的重均分子量为300以上20000以下。7. The photosensitive resin composition according to 5. or 6., wherein the weight average molecular weight of the novolak-type phenolic resin is 300 to 20,000.
8.根据5.至7.中任一项所述的感光性树脂组合物，其包含具备上述式(6)所示的重复单元的酸酐部位与上述酚醛清漆型酚醛树脂所具备的酚性羟基经由酯键键合而成的化合物。8. The photosensitive resin composition according to any one of 5. to 7., comprising an acid anhydride moiety having a repeating unit represented by the above-mentioned formula (6) and a phenolic hydroxyl group possessed by the novolac-type phenolic resin. Compounds bonded via ester bonds.
9.根据5.至8.中任一项所述的感光性树脂组合物，其中，上述聚合物还含有以下式(2)所示的重复单元或以下式(3)所示的重复单元。9. The photosensitive resin composition according to any one of 5. to 8., wherein the polymer further contains a repeating unit represented by the following formula (2) or a repeating unit represented by the following formula (3).
(式(2)中，R1、R2、R3和R4分别独立地为氢或碳原子数1～30的有机基团。n为0、1或2。)(In formula (2), R1 , R2 , R3 and R4 are each independently hydrogen or an organic group with 1 to 30 carbon atoms. n is 0, 1 or 2.)
(式(3)中，Ra分别独立地为碳原子数1～30的有机基团。m为0以上5以下的整数。)(In formula (3), Ra is each independently an organic group having 1 to 30 carbon atoms. m is an integer of 0 to 5.)
10.一种由5.至9.中任一项所述的感光性树脂组合物的固化物构成的树脂膜。10. A resin film comprising a cured product of the photosensitive resin composition described in any one of 5. to 9.
11.一种具备10.所述的树脂膜的电子装置。11. An electronic device comprising the resin film according to 10.
实施例Example
接着，对本发明的实施例进行说明。Next, examples of the present invention will be described.
首先，关于实施例所使用的各材料，如下所述进行准备。First, each material used in the examples was prepared as follows.
(酚醛清漆型酚醛树脂1)(Novolac type phenolic resin 1)
在具备搅拌装置、温度计、热交换器的3L的四口烧瓶中，相对于间甲酚与对甲酚以摩尔比(间甲酚:对甲酚)＝5:5的比率混合而成的酚类1000份，添加37％福尔马林水溶液526份(甲醛/酚的摩尔比＝0.70)、草酸10份，在回流下进行6小时反应。之后，在常压下进行脱水直至内温170℃，并在8.0kPa的减压下升温至230℃进行减压脱水，得到重均分子量11,000、分散度9.0、未反应酚类0.5％的酚醛清漆型酚醛树脂1050份。Phenol mixed with m-cresol and p-cresol at a molar ratio (m-cresol: p-cresol) = 5:5 in a 3 L four-necked flask equipped with a stirring device, a thermometer, and a heat exchanger To 1000 parts, 526 parts of 37% formalin aqueous solution (molar ratio of formaldehyde/phenol = 0.70) and 10 parts of oxalic acid were added, and the reaction was carried out under reflux for 6 hours. Afterwards, dehydration is carried out under normal pressure until the internal temperature is 170°C, and the temperature is raised to 230°C under a reduced pressure of 8.0kPa to perform dehydration under reduced pressure to obtain a novolac with a weight average molecular weight of 11,000, a degree of dispersion of 9.0, and 0.5% of unreacted phenols Type phenolic resin 1050 parts.
(聚合物1)(Polymer 1)
在具备搅拌机、冷却管的适当尺寸的反应容器中，称量马来酸酐(735g，7.5mol)、2-降冰片烯(706g，7.5mol)和2,2'-偶氮双(2-甲基丙酸)二甲酯(69g，0.3mol)，并溶解在甲基乙基酮和甲苯中。对该溶解液，通过氮鼓泡将体系内的溶解氧去除后，一边搅拌一边在60℃、15小时的条件下实施热处理。由此，得到2-降冰片烯与马来酸酐的共聚物。接着，使用大量甲醇使冷却至室温的上述溶解液再沉淀后，过滤析出物，利用真空干燥机使其干燥，得到1100g的白色固体。In an appropriately sized reaction vessel equipped with a stirrer, cooling tube, weigh maleic anhydride (735 g, 7.5 mol), 2-norbornene (706 g, 7.5 mol) and 2,2'-azobis(2-methane dimethyl propionate) (69 g, 0.3 mol) and dissolved in methyl ethyl ketone and toluene. After removing the dissolved oxygen in the system by nitrogen bubbling, this solution was heat-treated at 60° C. for 15 hours while stirring. Thus, a copolymer of 2-norbornene and maleic anhydride was obtained. Next, after reprecipitating the above-mentioned solution cooled to room temperature using a large amount of methanol, the precipitate was filtered and dried with a vacuum dryer to obtain 1100 g of a white solid.
以此方式得到的聚合物的重均分子量(Mw)为10,000，分散度(Mw/Mn)为2.1。The polymer obtained in this way had a weight average molecular weight (Mw) of 10,000 and a degree of dispersion (Mw/Mn) of 2.1.
(聚合物2)(Polymer 2)
准备苯乙烯/马来酸酐的共聚物SMA-1000-P(Cray Valley USA,LLC公司生产)。聚合物的重均分子量(Mw)为3,600，分散度(Mw/Mn)为2.3。A styrene/maleic anhydride copolymer SMA-1000-P (manufactured by Cray Valley USA, LLC) was prepared. The weight average molecular weight (Mw) of the polymer was 3,600, and the degree of dispersion (Mw/Mn) was 2.3.
(聚合物3)(Polymer 3)
在具备搅拌机、冷却管的适当尺寸的反应容器中，称量茚(870g，7.5mol)和2,2'-偶氮双(2-甲基丙酸)二甲酯(11.5g，0.05mol)，并溶解在甲基乙基酮中。对该溶解液，通过氮鼓泡将体系内的溶解氧去除后，一边搅拌，一边在达到70℃后从各口中历时5小时逐步添加马来酸酐(735g，7.5mol)甲基乙基酮溶液、正十二烷基硫醇(20.2g，0.10mol)甲基乙基酮溶液，之后进一步实施2小时热处理。由此，得到茚与马来酸酐的共聚物。In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, weigh indene (870 g, 7.5 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (11.5 g, 0.05 mol) , and dissolved in methyl ethyl ketone. After removing the dissolved oxygen in the system by nitrogen bubbling to the solution, while stirring, after reaching 70°C, gradually add maleic anhydride (735 g, 7.5 mol) methyl ethyl ketone solution from each mouth for 5 hours , n-dodecylmercaptan (20.2 g, 0.10 mol) methyl ethyl ketone solution, and then further heat-treating for 2 hours. Thus, a copolymer of indene and maleic anhydride was obtained.
(聚合物4)(Polymer 4)
在具备搅拌机、冷却管的适当尺寸的反应容器中，称量茚(870g，7.5mol)和2,2'-偶氮双(2-甲基丙酸)二甲酯(23.0g，0.1mol)，并溶解在甲基乙基酮中。对该溶解液，通过氮鼓泡将体系内的溶解氧去除后，一边搅拌，一边在达到75℃后历时6小时逐步添加柠康酸酐(840g，7.5mol)甲基乙基酮溶液，之后进一步实施3小时热处理。由此，得到茚与柠康酸酐的共聚物。In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, weigh indene (870 g, 7.5 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (23.0 g, 0.1 mol) , and dissolved in methyl ethyl ketone. To this solution, after the dissolved oxygen in the system was removed by nitrogen bubbling, while stirring, citraconic anhydride (840g, 7.5mol) methyl ethyl ketone solution was gradually added after reaching 75°C for 6 hours, and then further Heat treatment was carried out for 3 hours. Thus, a copolymer of indene and citraconic anhydride was obtained.
(聚合物5)(Polymer 5)
在具备搅拌机、冷却管的适当尺寸的反应容器中，称量茚(870g，7.5mol)和2,2'-偶氮双(2-甲基丙酸)二甲酯(11.5g，0.05mol)，并溶解在甲基乙基酮中。对该溶解液，通过氮鼓泡将体系内的溶解氧去除后，一边搅拌，一边在达到70℃后从各口中历时5小时逐步添加混合有马来酸酐(662g，6.75mol)和马来酰亚胺(72.8g，0.75mol)的甲基乙基酮溶液、正十二烷基硫醇(20.2g，0.10mol)甲基乙基酮溶液，之后进一步实施2小时热处理。由此，得到茚与马来酸酐、马来酰亚胺的共聚物。In an appropriately sized reaction vessel equipped with a stirrer and cooling tube, weigh indene (870 g, 7.5 mol) and dimethyl 2,2'-azobis(2-methylpropionate) (11.5 g, 0.05 mol) , and dissolved in methyl ethyl ketone. After removing the dissolved oxygen in the system by nitrogen bubbling to this solution, while stirring, after reaching 70° C., gradually add maleic anhydride (662 g, 6.75 mol) and maleic anhydride mixed with it from each port for 5 hours. A methyl ethyl ketone solution of an imine (72.8 g, 0.75 mol), a methyl ethyl ketone solution of n-dodecyl mercaptan (20.2 g, 0.10 mol), and then heat treatment was further performed for 2 hours. Thus, a copolymer of indene, maleic anhydride, and maleimide was obtained.
(聚合物6)(Polymer 6)
在具备搅拌机、冷却管的适当尺寸的反应容器中，称量茚(696g，6.0mol)、2-降冰片烯(141g，1.5mol)和2,2'-偶氮双(2-甲基丙酸)二甲酯(11.5g，0.05mol)，并溶解在甲基乙基酮中。对该溶解液，通过氮鼓泡将体系内的溶解氧去除后，一边搅拌，一边在达到70℃后从各口中历时7小时逐步添加马来酸酐(735g，7.5mol)甲基乙基酮溶液、正十二烷基硫醇(20.2g，0.10mol)甲基乙基酮溶液，之后进一步实施5小时热处理。由此，得到茚、降冰片烯与马来酸酐的共聚物。In an appropriately sized reaction vessel equipped with a stirrer and a cooling tube, weigh indene (696 g, 6.0 mol), 2-norbornene (141 g, 1.5 mol) and 2,2'-azobis(2-methylpropane acid) dimethyl ester (11.5 g, 0.05 mol), and dissolved in methyl ethyl ketone. After removing the dissolved oxygen in the system by bubbling nitrogen to the solution, while stirring, after reaching 70°C, a solution of methyl ethyl ketone (735 g, 7.5 mol) was gradually added from each port over a period of 7 hours. , n-dodecylmercaptan (20.2 g, 0.10 mol) methyl ethyl ketone solution, and then further heat-treating for 5 hours. Thus, a copolymer of indene, norbornene, and maleic anhydride was obtained.
(酚化合物1)(phenolic compound 1)
准备以下式所示的酚化合物(本州化学株式会社生产，制品名TrisP-PA)。A phenolic compound represented by the following formula (manufactured by Honshu Chemical Co., Ltd., product name TrisP-PA) was prepared.
(感光剂1)(Sensitizer 1)
准备以下式(B-1)所示的感光剂(DAITO CHEMIX Co.,Ltd.生产，制品名PA-28)。A sensitizer represented by the following formula (B-1) (manufactured by DAITO CHEMIX Co., Ltd., product name PA-28) was prepared.
其中，式(B-1)中的Q为氢原子或由上述式(B-2)表示，全部Q中90％为上述式(B-2)。Among them, Q in the formula (B-1) is a hydrogen atom or represented by the above formula (B-2), and 90% of all Q is the above formula (B-2).
(表面活性剂1)(surfactant 1)
准备氟系表面活性剂MEGAFACE F-556(DIC株式会社生产)。A fluorine-based surfactant MEGAFACE F-556 (manufactured by DIC Corporation) was prepared.
[感光性树脂组合物的制备][Preparation of Photosensitive Resin Composition]
关于各实施例和各比较例，准备表1和表2所示的量的各原料，溶解于PGMEA(丙二醇单甲醚乙酸酯)中，之后，利用孔径为0.2μm的氟树脂制过滤器进行过滤，得到感光性树脂组合物。For each example and each comparative example, each raw material in the amount shown in Table 1 and Table 2 was prepared, dissolved in PGMEA (propylene glycol monomethyl ether acetate), and thereafter, a filter made of fluororesin with a pore size of 0.2 μm was used. Filtration was performed to obtain a photosensitive resin composition.
另外，在制备各实施例和各比较例的感光性树脂组合物时，调整PGMEA(丙二醇单甲醚乙酸酯)使得树脂成分的含量(酚醛清漆型酚醛树脂与聚合物或酚化合物的总和)达到25％。In addition, when preparing the photosensitive resin composition of each Example and each comparative example, PGMEA (propylene glycol monomethyl ether acetate) was adjusted so that the content of the resin component (the sum of the novolac type phenolic resin and the polymer or phenolic compound) up to 25%.
另外，在各实施例中，关于实施例1和2，在酚醛清漆型酚醛树脂与聚合物1的甲基乙基酮溶液中进一步添加甲基乙基酮，再添加吡啶5质量份，以70℃加热2天后，去除溶剂、吡啶后，利用过滤器过滤进行制备。In addition, in each example, regarding Examples 1 and 2, methyl ethyl ketone was further added to the methyl ethyl ketone solution of the novolac type phenolic resin and the polymer 1, and then 5 parts by mass of pyridine was added to obtain a 70 After heating at °C for 2 days, the solvent and pyridine were removed, followed by filtration with a filter to prepare.
并且，关于实施例6～11，在酚醛清漆型酚醛树脂与聚合物3溶液的甲基乙基酮溶液中进一步添加甲基乙基酮、吡啶5质量份，以70℃反应3天后，去除反应溶剂、吡啶。In addition, regarding Examples 6 to 11, 5 parts by mass of methyl ethyl ketone and pyridine were further added to the methyl ethyl ketone solution of the novolac type phenolic resin and the polymer 3 solution, and after reacting at 70° C. for 3 days, the reaction was removed. Solvent, pyridine.
关于实施例13、14、15，在酚醛清漆型酚醛树脂和与各实施例对应的聚合物溶液4、5、6中，进一步添加甲基乙基酮、吡啶5质量份，以70℃反应3天后，去除反应溶剂、吡啶。Regarding Examples 13, 14, and 15, 5 parts by mass of methyl ethyl ketone and pyridine were further added to the novolak-type phenolic resin and the polymer solutions 4, 5, and 6 corresponding to each example, and 3 parts by mass of methyl ethyl ketone and pyridine were added to react at 70°C After 2 days, the reaction solvent, pyridine, was removed.
另外，关于实施例3～5、12、比较例1～2，与上述实施例1～2、6～11、13～15不同，在使各原料溶解于PGMEA之前，不使酚醛清漆型酚醛树脂与聚合物反应。In addition, regarding Examples 3-5, 12, and Comparative Examples 1-2, unlike the above-mentioned Examples 1-2, 6-11, 13-15, before dissolving each raw material in PGMEA, no novolak-type phenolic resin was used. Reacts with polymers.
依照以下项目对如上所述得到的感光性树脂组合物进行评价。The photosensitive resin composition obtained above was evaluated according to the following items.
(感光度)(sensitivity)
使用旋涂机将上述得到的感光性树脂组合物分别涂布于4英寸的硅晶片上，之后，利用加热板以110℃预烘烤2分钟，得到膜厚约2μm的涂覆膜。对该涂覆膜，通过凸版印刷株式会社生产的掩模(测试图No.1：描绘有宽度0.88～50μm的残留图案及镂空图案)，使用i线曝光机(尼康株式会社生产，NSR-4425i)改变曝光量进行照射。The above-obtained photosensitive resin composition was coated on a 4-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 110° C. for 2 minutes to obtain a coating film with a film thickness of about 2 μm. The coating film was passed through a mask produced by Toppan Printing Co., Ltd. (test pattern No. 1: a residual pattern and a hollow pattern with a width of 0.88 to 50 μm were drawn), and an i-line exposure machine (manufactured by Nikon Corporation, NSR-4425i ) to change the exposure for irradiation.
接着，使用2.38％的氢氧化四甲铵水溶液作为显影液，调节显影时间使得预烘烤后的膜厚与显影后的膜厚之差达到1.0μm，进行两次浸渍显影，由此将曝光部溶解去除，之后利用纯水冲洗10秒钟。将形成有100μm的正方形的通孔图案的最低曝光量的值评价为感光度。结果示于表1和表2。Next, use 2.38% tetramethylammonium hydroxide aqueous solution as the developer, adjust the development time so that the difference between the film thickness after prebaking and the film thickness after development reaches 1.0 μm, and perform two immersion developments, whereby the exposed part Dissolve and remove, then rinse with pure water for 10 seconds. The sensitivity was evaluated as the value of the lowest exposure amount in which a 100 μm square via hole pattern was formed. The results are shown in Table 1 and Table 2.
(耐热性评价)(Heat resistance evaluation)
使用旋涂机将上述得到的感光性树脂组合物分别涂布于4英寸的硅晶片上，之后，利用加热板以110℃预烘烤2分钟，得到膜厚约2μm的涂覆膜。对该涂覆膜，通过凸版印刷株式会社生产的掩模(1mm□的残留图案)，使用SUSS MicroTec公司生产的Mask AlignerMA8，将曝光时间固定为40秒进行曝光。接着，通过浸渍在2.38％的氢氧化四甲铵水溶液中，将曝光部溶解去除，之后利用纯水冲洗30秒钟。此时，未曝光部的膜减少量约为0.02μm。关于上述进行图案加工后的未曝光部，以100℃、1分钟的条件进行干燥，得到树脂膜。The above-obtained photosensitive resin composition was coated on a 4-inch silicon wafer using a spin coater, and then prebaked on a hot plate at 110° C. for 2 minutes to obtain a coating film with a film thickness of about 2 μm. This coating film was exposed through a mask (1 mm□ residual pattern) produced by Toppan Printing Co., Ltd., using Mask Aligner MA8 produced by SUSS MicroTec Co., Ltd., and the exposure time was fixed at 40 seconds. Next, the exposed portion was dissolved and removed by immersion in a 2.38% tetramethylammonium hydroxide aqueous solution, and then rinsed with pure water for 30 seconds. At this time, the amount of film reduction in the unexposed portion was about 0.02 μm. About the unexposed part after the said pattern processing, it dried on the conditions of 100 degreeC and 1 minute, and obtained the resin film.
关于该树脂膜，以140℃、3分钟的条件进行加热处理，使用金属显微镜，观察树脂膜的形状是否发生变化。另外，本试验中的评价基准如下。结果示于表1和表2。About this resin film, it heat-processed on the conditions of 140 degreeC and 3 minutes, and observed whether the shape of the resin film changed using the metal microscope. In addition, the evaluation criteria in this test are as follows. The results are shown in Table 1 and Table 2.
◎：未观察到图案的形状变化。⊚: No change in the shape of the pattern was observed.
○：虽然在图案的角部能够观察到略微的变形，但实际应用上没有问题的水准。◯: Although slight deformation is observed at the corners of the pattern, there is no problematic level in practical use.
×：观察到图案的形状变化。×: A shape change of the pattern is observed.
[表1][Table 1]
[表2][Table 2]
如表1和表2所示，在各实施例中，得到了能够耐受高温的树脂膜。并且，各实施例中所得到的各种感光性树脂组合物的感光度也高，被认定作为光致抗蚀剂的有用性高。As shown in Table 1 and Table 2, in each example, a resin film capable of withstanding high temperatures was obtained. Moreover, the sensitivity of various photosensitive resin compositions obtained in each Example was also high, and it was recognized that the usefulness as a photoresist is high.
另外，各实施例中，关于实施例1和实施例4，确认即便将耐热性试验的条件变更为150℃、3分钟的条件，也能够充分地保持图案形状。Moreover, in each Example, about Example 1 and Example 4, it was confirmed that even if the conditions of the heat resistance test were changed to the conditions of 150 degreeC and 3 minutes, the pattern shape was fully maintained.
另外，关于本实施例的感光性树脂组合物显示出高的耐热性，可以认为表现该耐热性的原因之一在于酚醛清漆型酚醛树脂与含有分子内具有环状结构的不饱和羧酸酐单元的特定的聚合物通过酯键牢固地交联。In addition, the photosensitive resin composition of this example shows high heat resistance, and it is considered that one of the reasons for showing this heat resistance is that novolac type phenolic resin and unsaturated carboxylic acid anhydride containing a ring structure in the molecule Units of specific polymers are strongly crosslinked by ester linkages.
在图2中表示上述聚合物2的FT-IR谱(图2(a))和如下组合物的FT-IR谱(图2(b))，该组合物是将聚合物2与酚醛清漆型酚醛树脂以25:75的比率溶解在甲基乙基酮中，在吡啶存在下以70℃反应1天，之后去除溶剂、吡啶后得到的组合物。由图2(a)与图2(b)比较可知，在图2(b)中，在酯键所特有的1700cm－1附近观察到吸收峰。In Fig. 2, the FT-IR spectrum of the above-mentioned polymer 2 (Fig. 2(a)) and the FT-IR spectrum of the following composition (Fig. 2(b)) are shown. A composition obtained by dissolving phenolic resin in methyl ethyl ketone at a ratio of 25:75, reacting at 70° C. for 1 day in the presence of pyridine, and then removing the solvent and pyridine. Comparing Fig. 2(a) with Fig. 2(b), it can be seen that in Fig. 2(b), an absorption peak is observed around 1700 cm-1 which is peculiar to an ester bond.
即，在本发明中，提示了这种酚醛树脂与分子内具有环状结构的不饱和羧酸酐单元的键有助于耐热性。That is, in the present invention, it is suggested that the bond between such a phenolic resin and an unsaturated carboxylic anhydride unit having a ring structure in the molecule contributes to heat resistance.
产业上的可利用性Industrial availability
本发明的树脂组合物基于酚醛树脂与具有特定的结构单元的聚合物的相互作用，能够表现出高耐热性，例如在制成感光性树脂组合物时，能够平衡性良好地表现出优异的感光度和高耐热性。The resin composition of the present invention is based on the interaction between the phenolic resin and the polymer having a specific structural unit, and can exhibit high heat resistance. For example, when it is made into a photosensitive resin composition, it can exhibit excellent heat resistance with good balance. Light sensitivity and high heat resistance.
并且，本发明的树脂组合物在除了这种感光性树脂组合物以外的用途中，还能够适当应用于要求耐热性的用途。In addition, the resin composition of the present invention can be suitably applied to applications requiring heat resistance in applications other than the photosensitive resin composition.
本申请主张基于2015年8月21日在日本提出的日本特愿2015-163438号的优先权，并将其公开的全部内容引用于此。This application claims priority based on Japanese Patent Application No. 2015-163438 for which it applied in Japan on August 21, 2015, and uses the whole content of the indication here.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015163438 | 2015-08-21 | ||
| JP2015-163438 | 2015-08-21 | ||
| PCT/JP2016/071401WO2017033633A1 (en) | 2015-08-21 | 2016-07-21 | Resin composition, photosensitive resin composition, resin film and electronic device |
| Publication Number | Publication Date |
|---|---|
| CN107922708Atrue CN107922708A (en) | 2018-04-17 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680048062.7APendingCN107922708A (en) | 2015-08-21 | 2016-07-21 | Resin composition, photosensitive resin composition, resin film and electronic device |
| Country | Link |
|---|---|
| JP (3) | JP6354802B2 (en) |
| KR (1) | KR101927037B1 (en) |
| CN (1) | CN107922708A (en) |
| TW (1) | TWI694098B (en) |
| WO (1) | WO2017033633A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511532A (en)* | 2019-09-25 | 2019-11-29 | 河南工业大学 | A kind of maleic anhydride-acrylate copolymer modified phenolic resin |
| CN113811556A (en)* | 2019-05-08 | 2021-12-17 | 住友电木株式会社 | Photosensitive resin composition, resin film, and electronic device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018061584A1 (en)* | 2016-09-28 | 2018-04-05 | 住友ベークライト株式会社 | Phenol resin composition for friction material and friction material |
| JP7088640B2 (en)* | 2017-08-01 | 2022-06-21 | 旭化成株式会社 | Semiconductor devices and their manufacturing methods |
| JP7043756B2 (en)* | 2017-08-31 | 2022-03-30 | 住友ベークライト株式会社 | Photosensitive resin composition, pattern forming method, electronic device manufacturing method, polymer and polymer manufacturing method |
| JP7020018B2 (en)* | 2017-09-15 | 2022-02-16 | 住友ベークライト株式会社 | Rubber composition |
| JP6764885B2 (en)* | 2018-01-11 | 2020-10-07 | Ｊｆｅケミカル株式会社 | Thermosetting resin composition and its cured product |
| JP6950573B2 (en)* | 2018-02-26 | 2021-10-13 | Jnc株式会社 | Thermosetting composition |
| JP7559421B2 (en)* | 2020-03-02 | 2024-10-02 | 住友ベークライト株式会社 | Polymer solution for forming color filters or black matrices |
| KR20230071160A (en)* | 2020-09-23 | 2023-05-23 | 스미또모 베이크라이트 가부시키가이샤 | Polymers, polymer solutions and photosensitive resin compositions |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6416925B1 (en)* | 1997-02-18 | 2002-07-09 | Fuji Photo Film Co., Ltd. | Positive working photosensitive composition |
| US6534235B1 (en)* | 2000-10-31 | 2003-03-18 | Kansai Research Institute, Inc. | Photosensitive resin composition and process for forming pattern |
| CN1500119A (en)* | 2001-02-26 | 2004-05-26 | 音思万有限公司 | Positive photodefinable compsn. of polycarboxylic acid, phenolic and thermocurable resins |
| CN103370347A (en)* | 2010-11-24 | 2013-10-23 | 普罗米鲁斯有限责任公司 | A self-imageable film forming polymer, compositions thereof and devices and structures made therefrom |
| CN104216222A (en)* | 2013-05-29 | 2014-12-17 | 住友电木株式会社 | Photosensitive resin composition and electronic device |
| CN104216228A (en)* | 2013-05-29 | 2014-12-17 | 住友电木株式会社 | Negative photosensitive resin composition, electronic device and polymer |
| JP5672403B1 (en)* | 2014-05-26 | 2015-02-18 | 住友ベークライト株式会社 | Photosensitive resin composition and electronic device |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595243A (en)* | 1982-07-02 | 1984-01-12 | Hitachi Ltd | Radiation sensitive composition and formation of pattern |
| US5110700A (en)* | 1990-12-28 | 1992-05-05 | Xerox Corporation | Electrophotographic imaging member |
| JPH06305076A (en)* | 1993-04-26 | 1994-11-01 | Hitachi Chem Co Ltd | Production of metal base melamine resin decorative panel |
| JP3429852B2 (en)* | 1993-06-04 | 2003-07-28 | シップレーカンパニー エル エル シー | Negative photosensitive composition |
| CA2211652C (en)* | 1995-01-27 | 2008-03-25 | Frank W. Mercer | Gels from anhydride-containing polymers |
| JP3944966B2 (en)* | 1996-09-30 | 2007-07-18 | 日本ゼオン株式会社 | Modified norbornene polymer and method for producing the same |
| JP2000122278A (en)* | 1998-10-21 | 2000-04-28 | Okamoto Kagaku Kogyo Kk | Photosensitive composition and photosensitive planographic printing plate |
| JP3615981B2 (en)* | 1999-11-24 | 2005-02-02 | クラリアント インターナショナル リミテッド | Photosensitive resin composition |
| US6449918B1 (en)* | 1999-11-08 | 2002-09-17 | Premark Rwp Holdings, Inc. | Multipanel floor system panel connector with seal |
| CN1717630A (en)* | 2003-06-30 | 2006-01-04 | 株式会社新克 | Positive photosensitive composition |
| JP2005105209A (en)* | 2003-10-01 | 2005-04-21 | Yokohama Rubber Co Ltd:The | Highly damping elastomer composition |
| JP4951200B2 (en)* | 2004-08-20 | 2012-06-13 | 東洋インキＳｃホールディングス株式会社 | Color filter |
| JP2015166431A (en)* | 2014-03-04 | 2015-09-24 | 日立化成株式会社 | Thermosetting resin composition, prepreg and laminated plate |
| JP6287652B2 (en)* | 2014-07-10 | 2018-03-07 | 日油株式会社 | Photosensitive resin composition and use thereof |
| JP6528421B2 (en)* | 2015-01-28 | 2019-06-12 | 住友ベークライト株式会社 | Photosensitive resin composition |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6416925B1 (en)* | 1997-02-18 | 2002-07-09 | Fuji Photo Film Co., Ltd. | Positive working photosensitive composition |
| US6534235B1 (en)* | 2000-10-31 | 2003-03-18 | Kansai Research Institute, Inc. | Photosensitive resin composition and process for forming pattern |
| CN1500119A (en)* | 2001-02-26 | 2004-05-26 | 音思万有限公司 | Positive photodefinable compsn. of polycarboxylic acid, phenolic and thermocurable resins |
| CN103370347A (en)* | 2010-11-24 | 2013-10-23 | 普罗米鲁斯有限责任公司 | A self-imageable film forming polymer, compositions thereof and devices and structures made therefrom |
| CN104216222A (en)* | 2013-05-29 | 2014-12-17 | 住友电木株式会社 | Photosensitive resin composition and electronic device |
| CN104216228A (en)* | 2013-05-29 | 2014-12-17 | 住友电木株式会社 | Negative photosensitive resin composition, electronic device and polymer |
| JP5672403B1 (en)* | 2014-05-26 | 2015-02-18 | 住友ベークライト株式会社 | Photosensitive resin composition and electronic device |
| Title |
|---|
| 俞铁铭 等: "《精细有机单元反应与工艺》", 31 January 2015, 浙江大学出版社* |
| 段行信: "《实用精细有机合成手册》", 31 January 2000, 化学工业出版社* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113811556A (en)* | 2019-05-08 | 2021-12-17 | 住友电木株式会社 | Photosensitive resin composition, resin film, and electronic device |
| CN113811556B (en)* | 2019-05-08 | 2024-05-28 | 住友电木株式会社 | Photosensitive resin composition, resin film and electronic device |
| CN110511532A (en)* | 2019-09-25 | 2019-11-29 | 河南工业大学 | A kind of maleic anhydride-acrylate copolymer modified phenolic resin |
| CN110511532B (en)* | 2019-09-25 | 2022-03-25 | 河南工业大学 | A kind of maleic anhydride-acrylate copolymer modified phenolic resin |
| Publication number | Publication date |
|---|---|
| KR101927037B1 (en) | 2018-12-07 |
| JP2018109196A (en) | 2018-07-12 |
| WO2017033633A1 (en) | 2017-03-02 |
| JP6468393B2 (en) | 2019-02-13 |
| KR20180031804A (en) | 2018-03-28 |
| JP2017039909A (en) | 2017-02-23 |
| TW201718719A (en) | 2017-06-01 |
| JP6414352B2 (en) | 2018-10-31 |
| JP6354802B2 (en) | 2018-07-11 |
| TWI694098B (en) | 2020-05-21 |
| JP2018172700A (en) | 2018-11-08 |
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|---|---|---|
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| Date | Code | Title | Description |
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| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | Application publication date:20180417 |