TW202311306A - Negative photosensitive resin composition, negative photosensitive polymer, cured film and semiconductor device - Google Patents
Negative photosensitive resin composition, negative photosensitive polymer, cured film and semiconductor device Download PDFInfo
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Abstract
Description
本發明係有關一種負型感光性樹脂組成物、負型感光性聚合物、硬化膜及半導體裝置。The invention relates to a negative photosensitive resin composition, a negative photosensitive polymer, a cured film and a semiconductor device.
聚醯亞胺樹脂具有高機械強度、耐熱性、絕緣性、耐溶劑性，因此作為液晶顯示元件或半導體中之保護材料、絕緣材料、濾色器等的電子材料用薄膜而廣泛使用。Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as protective materials in liquid crystal display elements and semiconductors, insulating materials, and films for electronic materials such as color filters.
在專利文獻1中，揭示有一種可溶於雙極性非質子性溶劑中之嵌段共聚型聚醯亞胺，並且記載為能夠使用特定的酸酐來獲得嵌段共聚型聚醯亞胺。Patent Document 1 discloses a block-copolymerizable polyimide soluble in a bipolar aprotic solvent, and describes that the block-copolymerizable polyimide can be obtained using a specific acid anhydride.
在專利文獻2中，揭示有一種由具有特定結構之構成單元構成之聚醯亞胺樹脂。在專利文獻2中，記載有使用4,4-二胺基-3,3-二乙基-5,5-二甲基二苯基甲烷合成了聚醯亞胺樹脂之例。Patent Document 2 discloses a polyimide resin composed of structural units having a specific structure. Patent Document 2 describes an example in which a polyimide resin was synthesized using 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane.
在專利文獻3中，揭示有一種聚醯亞胺彈性體樹脂，其為由芳香族四羧酸二酐、在具有胺基之芳香環中具有至少1個以上的烷基之4,4′-二胺基二苯基甲烷及在兩個末端具有對胺基苯甲酸酯基之聚醚低聚物獲得之三元共聚物（Terpolymer），並且具有特定分子量。在專利文獻3中，作為4,4′-二胺基二苯基甲烷，可以舉出雙（4-胺基-3-乙基-5-甲基苯基）甲烷。在專利文獻3中，記載為該樹脂的耐熱濕性優異。In Patent Document 3, a polyimide elastomer resin is disclosed, which is composed of aromatic tetracarboxylic dianhydride, 4,4'- Terpolymer obtained from diaminodiphenylmethane and polyether oligomers with p-aminobenzoate groups at both ends, and has a specific molecular weight. In Patent Document 3, bis(4-amino-3-ethyl-5-methylphenyl)methane is mentioned as 4,4'-diaminodiphenylmethane. Patent Document 3 describes that this resin is excellent in heat and humidity resistance.
在專利文獻4中，揭示有一種由聚醯亞胺結構單元和二甲基矽氧烷結構單元構成之嵌段共聚物，該聚醯亞胺結構單元由芳香族四羧酸二酐和4,4′-二胺基二苯基甲烷衍生物形成。在專利文獻4中，作為4,4′-二胺基二苯基甲烷，可以舉出雙（4-胺基-3-乙基-5-甲基苯基）甲烷。在專利文獻4中，記載為該樹脂的耐熱性或溶劑溶解性優異。 [先前技術文獻] [專利文獻] In Patent Document 4, a block copolymer composed of polyimide structural unit and dimethylsiloxane structural unit is disclosed, the polyimide structural unit is composed of aromatic tetracarboxylic dianhydride and 4, 4'-Diaminodiphenylmethane derivatives are formed. In Patent Document 4, bis(4-amino-3-ethyl-5-methylphenyl)methane is mentioned as 4,4'-diaminodiphenylmethane. Patent Document 4 describes that the resin is excellent in heat resistance and solvent solubility. [Prior Art Literature] [Patent Document]
〔專利文獻1〕國際公開第015/091122號 〔專利文獻2〕日本特開昭64-16829號公報 〔專利文獻3〕日本特開平8-217874號公報 〔專利文獻4〕日本特開平9-40777號公報 [Patent Document 1] International Publication No. 015/091122 [Patent Document 2] Japanese Patent Laid-Open No. 64-16829 [Patent Document 3] Japanese Patent Application Laid-Open No. 8-217874 [Patent Document 4] Japanese Patent Application Laid-Open No. 9-40777
[發明所欲解決之課題][Problem to be Solved by the Invention]
然而，在專利文獻1～4中所記載的以往的技術中，在包含由感光性樹脂組成物獲得之聚醯亞胺之膜的伸長率等機械強度存在改善的餘地。However, in the conventional techniques described in Patent Documents 1 to 4, there is room for improvement in mechanical strength such as elongation of a film made of polyimide obtained from a photosensitive resin composition.
自往，為了改善聚醯亞胺對有機溶劑的溶解性，在該聚醯亞胺的骨架中導入氟原子，然而，本發明人等發現了下述情況：在使用包含氟原子之二胺化合物合成了聚醯亞胺之情況，由於因氟原子的強吸電子性而對醯亞胺環的電子造成影響，所獲得之聚醯亞胺容易被水解，因此伸長率等機械強度降低。 亦即，就對有機溶劑的溶解性與伸長率等機械強度的平衡的觀點而言，以往的聚醯亞胺存在改善的餘地。 [解決課題之技術手段] Conventionally, in order to improve the solubility of polyimide in organic solvents, fluorine atoms were introduced into the polyimide skeleton. In the case of synthesizing polyimide, since the electrons of the imide ring are affected by the strong electron-attracting property of the fluorine atom, the obtained polyimide is easily hydrolyzed, and thus the mechanical strength such as elongation decreases. That is, conventional polyimides have room for improvement from the viewpoint of the balance between solubility in organic solvents and mechanical strength such as elongation. [Technical means to solve the problem]
本發明人等發現只要為具備特定結構之聚醯亞胺，則能夠解決上述課題，從而完成了本發明。 亦即，本發明能夠如下所示。 The inventors of the present invention have found that the above-mentioned problems can be solved as long as the polyimide has a specific structure, and completed the present invention. That is, the present invention can be as follows.
[1]一種負型感光性樹脂組成物，其包含（A）聚醯亞胺、（B）包含多官能（甲基）丙烯酸酯之交聯劑及（C）光聚合起始劑，
聚醯亞胺（A）包含下述通式（a1）所表示之結構單元（a1）、下述通式（a2）所表示之結構單元（a2）及下述通式（a3）所表示之結構單元（a3）。
以下，使用圖式對本發明的實施形態進行說明。再者，在所有圖式中，對相同的構成要素標註相同的符號，並適當省略說明。又，除非另有說明，則「A～B」表示「A以上」至「B以下」。 本實施形態的負型感光性樹脂組成物包含（A）聚醯亞胺、（B）包含多官能（甲基）丙烯酸酯之交聯劑及（C）光聚合起始劑。 Hereinafter, embodiments of the present invention will be described using the drawings. In addition, in all drawings, the same code|symbol is attached|subjected to the same component, and description is abbreviate|omitted suitably. Also, "A to B" means "above A" to "below B" unless otherwise specified. The negative photosensitive resin composition of the present embodiment includes (A) polyimide, (B) a crosslinking agent including polyfunctional (meth)acrylate, and (C) a photopolymerization initiator.
[聚醯亞胺（A）] 關於本實施形態的聚醯亞胺（A）（負型感光性聚合物），能夠藉由第1實施形態或第2實施形態進行說明。 [Polyimide (A)] The polyimide (A) (negative photosensitive polymer) of this embodiment can be demonstrated using 1st Embodiment or 2nd Embodiment.
（第1實施形態） 本實施形態的聚醯亞胺（A）（負型感光性聚合物）包含下述通式（a1）所表示之結構單元（a1）、下述通式（a2）所表示之結構單元（a2）及下述通式（a3）所表示之結構單元（a3）。 (first embodiment) The polyimide (A) (negative photosensitive polymer) of this embodiment includes the structural unit (a1) represented by the following general formula (a1), the structural unit (a2) represented by the following general formula (a2) ) and the structural unit (a3) represented by the following general formula (a3).
通式（a1）中，Y為2價的有機基。 作為2價的有機基，能夠在發揮本發明的效果之範圍使用公知的有機基，然而，就本發明的效果的觀點而言，Y為包含伸烷基之2價的基或包含至少1個芳香環之2價的基為較佳。 作為伸烷基，較佳為碳數1～5的伸烷基，更佳為碳數1～3的伸烷基。作為芳香環，可以舉出2價的苯環、2價的萘環、2價的蒽環、2價的聯苯基等，2價的苯環或2價的聯苯基為較佳。 通式（a1）中的Y為選自下述通式（a1-1）、下述通式（a1-2）及下述通式（a1-3）之2價的有機基為較佳。 In the general formula (a1), Y is a divalent organic group. As the divalent organic group, known organic groups can be used within the scope of exerting the effect of the present invention, however, from the viewpoint of the effect of the present invention, Y is a divalent group containing an alkylene group or containing at least one A divalent group of an aromatic ring is preferable. The alkylene group is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the aromatic ring include a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, and a divalent biphenyl group. A divalent benzene ring or a divalent biphenyl group is preferred. Y in the general formula (a1) is preferably a divalent organic group selected from the following general formula (a1-1), the following general formula (a1-2) and the following general formula (a1-3).
通式（a1-1）中，R 7及R 8分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R 7彼此及存在複數個之R 8彼此可以相同，亦可以不同。 就本發明的效果的觀點而言，R 7及R 8較佳為氫原子或碳數1～3的烷基，更佳為氫原子。 In the general formula (a1-1), R 7 and R 8 independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R 7 and each other and there are plural Each of R 8 may be the same as or different from each other. From the viewpoint of the effects of the present invention, R 7 and R 8 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom.
R 9表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R 9彼此可以相同，亦可以不同。 就本發明的效果的觀點而言，R 9較佳為氫原子或碳數1～3的烷基，更佳為氫原子。 *表示鍵結鍵。 R 9 represents a hydrogen atom, an alkyl group having 1 to 3 carbons, and an alkoxy group having 1 to 3 carbons, and a plurality of R 9 may be the same or different from each other. From the viewpoint of the effects of the present invention, R 9 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably a hydrogen atom. * Indicates a bonded bond.
通式（a1-2）中，R 10及R 11分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基，存在複數個之R 10彼此及存在複數個之R 11彼此可以相同，亦可以不同。 In the general formula (a1-2), R 10 and R 11 independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, and an alkoxy group with 1 to 3 carbons, and there are plural R 10s with each other and plural Each R 11 may be the same as or different from each other.
就本發明的效果的觀點而言，R 10及R 11較佳為氫原子或碳數1～3的烷基，更佳為R 10中的至少1個及R 11中的至少1個為碳數1～3的烷基，進而較佳為3個R 10為碳數1～3的烷基且1個R 10為氫原子，並且3個R 11為碳數1～3的烷基且1個R 11為氫原子，特佳為3個R 10為甲基且1個R 10為氫原子，並且3個R 11為甲基且1個R 11為氫原子。 *表示鍵結鍵。 From the viewpoint of the effects of the present invention, R 10 and R 11 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbons, more preferably at least one of R 10 and at least one of R 11 is carbon An alkyl group with a number of 1 to 3, more preferably three R 10 are an alkyl group with a carbon number of 1 to 3 and one R 10 is a hydrogen atom, and three R 11 are an alkyl group with a carbon number of 1 to 3 and 1 R 11 is a hydrogen atom, particularly preferably 3 R 10 is a methyl group and 1 R 10 is a hydrogen atom, and 3 R 11 is a methyl group and 1 R 11 is a hydrogen atom. * Indicates a bonded bond.
通式（a1-3）中，Z表示碳數1～5的伸烷基或2價的芳香族基，2價的芳香族基為較佳。作為2價的芳香族基，可以舉出2價的苯環、2價的萘環、2價的蒽環、2價的聯苯基，2價的苯環為較佳。 *表示鍵結鍵。 In the general formula (a1-3), Z represents an alkylene group having 1 to 5 carbon atoms or a divalent aromatic group, and a divalent aromatic group is preferable. Examples of the divalent aromatic group include a divalent benzene ring, a divalent naphthalene ring, a divalent anthracene ring, and a divalent biphenyl group, and a divalent benzene ring is preferred. * Indicates a bonded bond.
通式（a2）中，R 1～R 4分別獨立地表示碳數1～3的烷基或碳數1～3的烷氧基，R 1和R 2為不同之基，R 3和R 4為不同之基。 就本發明的效果的觀點而言，R 1～R 4較佳為碳數1～3的烷基。 In the general formula (a2), R 1 to R 4 independently represent an alkyl group with 1 to 3 carbons or an alkoxy group with 1 to 3 carbons, R 1 and R 2 are different groups, R 3 and R 4 as the basis of difference. From the viewpoint of the effect of the present invention, R 1 to R 4 are preferably an alkyl group having 1 to 3 carbon atoms.
X 1表示單鍵、-SO 2-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X 1可以相同，亦可以不同。 X 1 represents a single bond, -SO 2 -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X 1 which may be the same or different.
就本發明的效果的觀點而言，X 1較佳為單鍵、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，更佳為碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基。 From the viewpoint of the effects of the present invention, X is preferably a single bond, a straight-chain or branched chain alkylene group having 1 to 5 carbons, or a straight-chain or branched chain fluoroalkylene group having 1 to 5 carbons. , more preferably a straight chain or branched chain alkylene group having 1 to 5 carbons or a straight chain or branched chain fluoroalkylene group having 1 to 5 carbons.
藉由本實施形態的聚醯亞胺（A）包含通式（a2）所表示之結構單元，對醯亞胺環的電子的影響得到抑制而該聚醯亞胺的水解得到抑制，從而伸長率等機械強度優異，並且對有機溶劑的溶解性亦優異。換言之，本實施形態的聚醯亞胺（A）及包含聚醯亞胺（A）之負型感光性樹脂組成物的該等特性的平衡優異。Since the polyimide (A) of this embodiment includes the structural unit represented by the general formula (a2), the influence on the electrons of the imide ring is suppressed, and the hydrolysis of the polyimide is suppressed, so that elongation, etc. It is excellent in mechanical strength and also excellent in solubility to organic solvents. In other words, the polyimide (A) of this embodiment and the negative photosensitive resin composition containing the polyimide (A) are excellent in the balance of these characteristics.
通式（a3）中，Q表示2價～4價的碳數1～10的有機基，存在複數個之Q可以相同，亦可以不同。In the general formula (a3), Q represents a divalent to tetravalent organic group having 1 to 10 carbon atoms, and plural Qs may be the same or different.
作為2價～4價的碳數1～10的有機基，可以舉出酯基、2價～4價的碳數1～10的脂肪族烴基、2價～4價的碳數3～10的脂環式烴基等，該等烴基可以包含氧、氮、硫原子等雜原子，亦可以在結構中具有酯鍵、硫酯鍵、胺酯（urethane）鍵、硫胺酯鍵、脲鍵等。Examples of the divalent to tetravalent organic group having 1 to 10 carbon atoms include an ester group, a divalent to tetravalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a divalent to tetravalent organic group having 3 to 10 carbon atoms. Alicyclic hydrocarbon groups, etc. These hydrocarbon groups may contain heteroatoms such as oxygen, nitrogen, and sulfur atoms, and may also have ester bonds, thioester bonds, urethane bonds, thiamine ester bonds, urea bonds, etc. in the structure.
R 5及R 6分別獨立地表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基。 m1及m2分別獨立地表示1～3的整數。 R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbons, or an alkoxy group having 1 to 3 carbons. m1 and m2 each independently represent the integer of 1-3.
X 2表示單鍵、-SO 2-、-C(=O)-、碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基，存在複數個之X 2可以相同，亦可以不同。 X 2 represents a single bond, -SO 2 -, -C(=O)-, straight-chain or branched chain alkylene with 1 to 5 carbons, or straight-chain or branched fluoroalkylene with 1 to 5 carbons Base, there are plural X 2 which may be the same or different.
就本發明的效果的觀點而言，X 2為碳數1～5的直鏈或支鏈的伸烷基或者碳數1～5的直鏈或支鏈的氟伸烷基為較佳。 From the viewpoint of the effect of the present invention, X2 is preferably a straight-chain or branched chain alkylene group having 1 to 5 carbons or a straight chain or branched chain fluoroalkylene group having 1 to 5 carbons.
具體而言，本實施形態的聚醯亞胺（A）能夠包含下述通式（1）所表示之結構單元。Specifically, the polyimide (A) of this embodiment can contain the structural unit represented by following General formula (1).
通式（1）中，R 1～R 4、X 1與通式（a2）的含義相同，Y與通式（a1）的含義相同。 In the general formula (1), R 1 to R 4 and X 1 have the same meanings as those of the general formula (a2), and Y has the same meanings as those of the general formula (a1).
具體而言，本實施形態的聚醯亞胺（A）能夠包含上述通式（1）所表示之結構單元和下述通式（2）所表示之結構單元。Specifically, the polyimide (A) of this embodiment can contain the structural unit represented by the said general formula (1) and the structural unit represented by the following general formula (2).
通式（2）中，Q、R 5、R 6、m1、m2及X 2與通式（a3）的含義相同，Y與通式（a1）的含義相同。 In the general formula (2), Q, R 5 , R 6 , m1, m2 and X 2 have the same meaning as the general formula (a3), and Y has the same meaning as the general formula (a1).
具體而言，本實施形態的聚醯亞胺（A）能夠包含上述通式（3）所表示之結構單元。Specifically, the polyimide (A) of this embodiment can contain the structural unit represented by the said General formula (3).
通式（3）中，Q、R 5、R 6、m1、m2及X 2與通式（a3）的含義相同，Y與通式（a1）的含義相同，R 1～R 4、X 1與通式（a2）的含義相同。 In general formula (3), Q, R 5 , R 6 , m1, m2 and X 2 have the same meaning as general formula (a3), Y has the same meaning as general formula (a1), and R 1 ~ R 4 , X 1 It has the same meaning as the general formula (a2).
本實施形態的聚醯亞胺（A）可以包含前述結構單元，亦可以進一步在一部分中包含以下的結構單元。The polyimide (A) of this embodiment may contain the said structural unit, and may further contain the following structural unit partly.
該等通式中，Q、R 5、R 6、m1、m2及X 2與通式（a3）的含義相同，Y與通式（a1）的含義相同。 在本實施形態中，聚醯亞胺（A）的兩個末端中的至少一者為（甲基）丙烯酸酯基為較佳。藉由包含該基，伸長率等機械強度更加優異。能夠藉由 1H-NMR來分析出具有（甲基）丙烯酸酯基。 In these general formulas, Q, R 5 , R 6 , m1, m2 and X 2 have the same meaning as those of the general formula (a3), and Y has the same meaning as that of the general formula (a1). In this embodiment, it is preferable that at least one of both terminals of the polyimide (A) is a (meth)acrylate group. By including this group, the mechanical strength such as elongation becomes more excellent. It can be analyzed by 1 H-NMR that it has a (meth)acrylate group.
具體而言，聚醯亞胺（A）在兩個末端中的至少一者具備下述通式（a4）～下述通式（a12）所表示之末端結構（a4）～末端結構（a12）中的至少1個為較佳，具備末端結構（a4）為較佳。
通式（a4）中，Q與通式（a3）的含義相同，Y與通式（a1）的含義相同。R 7表示氫原子、碳數1～3的烷基、碳數1～3的烷氧基。 m3表示1～3的整數。*表示鍵結鍵。 通式（a5）中，Q與通式（a3）的含義相同，X 1、R 1～R 4與通式（a2）的含義相同。R 7、m3與通式（a4）的含義相同。*表示鍵結鍵。 通式（a6）～（a12）中，Q、R 5、R 6、m1、m2及X 2與通式（a3）的含義相同。R 7、m3與通式（a4）的含義相同。*表示鍵結鍵。 In general formula (a4), Q has the same meaning as general formula (a3), and Y has the same meaning as general formula (a1). R 7 represents a hydrogen atom, an alkyl group having 1 to 3 carbons, and an alkoxy group having 1 to 3 carbons. m3 represents the integer of 1-3. * Indicates a bonded bond. In the general formula (a5), Q has the same meaning as the general formula (a3), and X 1 , R 1 to R 4 have the same meanings as the general formula (a2). R 7 and m3 have the same meanings as in the general formula (a4). * Indicates a bonded bond. In the general formulas (a6) to (a12), Q, R 5 , R 6 , m1, m2 and X 2 have the same meanings as those in the general formula (a3). R 7 and m3 have the same meanings as in the general formula (a4). * Indicates a bonded bond.
本實施形態的聚醯亞胺（A）的重量平均分子量為5,000～200,000，較佳為10,000～100,000。The weight average molecular weight of the polyimide (A) of this embodiment is 5,000-200,000, Preferably it is 10,000-100,000.
本實施形態的聚醯亞胺（A）的水解得到抑制，聚醯亞胺（A）及包含聚醯亞胺（A）之負型感光性樹脂組成物能夠獲得伸長率等機械強度優異之膜等硬化物。 又，本實施形態的聚醯亞胺（A）對溶劑的溶解性優異，且無需在前驅物的狀態下製成清漆，因此能夠製備包含聚醯亞胺（A）之清漆，從而能夠由該清漆獲得膜等硬化物。 The hydrolysis of the polyimide (A) of this embodiment is suppressed, and the polyimide (A) and the negative photosensitive resin composition containing the polyimide (A) can obtain a film excellent in mechanical strength such as elongation Wait for hardening. In addition, the polyimide (A) of this embodiment has excellent solubility in solvents, and it is not necessary to prepare a varnish in the state of a precursor, so it is possible to prepare a varnish containing the polyimide (A), and it is possible to use this The varnish obtains a hardened product such as a film.
＜聚醯亞胺（A）之製造方法＞ 本實施形態的具有通式（1）所表示之結構單元及通式（2）所表示之結構單元之聚醯亞胺（A）（負型感光性聚合物）或具有通式（3）所表示之結構單元之聚醯亞胺（A）（負型感光性聚合物）之製造方法包括下述步驟： 步驟1，在100℃以上且250℃以下的溫度使下述通式（a1’）所表示之酸酐（a1’）、下述通式（a2’）所表示之二胺（a2’）及下述通式（a3’）所表示之雙胺基苯酚（a3’）醯亞胺化；及 步驟2，使具備（甲基）丙烯酸酯基之化合物與在步驟1中所獲得之聚合物的來自於前述通式（a3’）的雙胺基苯酚（a3’）的結構單元的羥基進行反應而導入包含（甲基）丙烯酸酯基之基。 依據本實施形態，能夠藉由簡單的方法來合成在有機溶劑中之溶解性優異之聚醯亞胺（A）。 ＜Method for producing polyimide (A)＞ The polyimide (A) (negative photosensitive polymer) having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in this embodiment or having the structural unit represented by the general formula (3) The manufacturing method of the polyimide (A) (negative photosensitive polymer) of the structural unit represented comprises the following steps: Step 1, the acid anhydride (a1') represented by the following general formula (a1'), the diamine (a2') represented by the following general formula (a2') and the following imidization of the bisaminophenol (a3') represented by the general formula (a3'); and Step 2, reacting a compound having a (meth)acrylate group with a hydroxyl group derived from a structural unit of the bisaminophenol (a3') of the aforementioned general formula (a3') of the polymer obtained in Step 1 Instead, a group including a (meth)acrylate group is introduced. According to this embodiment, the polyimide (A) excellent in the solubility to an organic solvent can be synthesize|combined by a simple method.
通式（a1’）中，Y與通式（a1）的含義相同，較佳為選自前述通式（a1-1）、（a1-2）或（a1-3）所表示之基。In the general formula (a1'), Y has the same meaning as the general formula (a1), and is preferably selected from the groups represented by the aforementioned general formula (a1-1), (a1-2) or (a1-3).
通式（a2’）中，R 1～R 4、X 1與通式（a2）的含義相同。 In general formula (a2'), R 1 to R 4 and X 1 have the same meanings as in general formula (a2).
通式（a3’）中，X 2與通式（a3）的含義相同。 In general formula (a3'), X 2 has the same meaning as general formula (a3).
為了控制所獲得之聚羥基醯亞胺的分子量，亦能夠添加少量的酸酐或芳香族胺作為封端劑進行反應。In order to control the molecular weight of the obtained polyhydroxyimide, it is also possible to add a small amount of acid anhydride or aromatic amine as an end-capping agent to react.
作為封端劑之酸酐，可以舉出酞酸酐、順丁烯二酸酐、納迪克酸酐（nadic anhydride）等，作為芳香族胺，可以舉出對甲基苯胺、對甲氧基苯胺、對苯氧基苯胺等。該等作為封端劑之酸酐或芳香族胺的添加量為5莫耳%以下為較佳。若超過5莫耳%，則所獲得之聚羥基醯亞胺的分子量會顯著降低而耐熱性或機械特性出現問題。Examples of the acid anhydride of the blocking agent include phthalic anhydride, maleic anhydride, and nadic anhydride, and examples of the aromatic amine include p-methylaniline, p-methoxyaniline, p-phenoxy Aniline, etc. The addition amount of these acid anhydrides or aromatic amines as end-capping agents is preferably less than 5 mol%. If it exceeds 5 mol %, the molecular weight of the obtained polyhydroxyimide is remarkably lowered to cause problems in heat resistance or mechanical properties.
步驟1的醯亞胺化反應中之酸酐（a1’）與二胺（a2’）與雙胺基苯酚（a3’）的當量比為決定所獲得之聚合物的分子量之重要因素。一般而言，在聚合物的分子量與機械性質之間存在相關性已廣為周知，分子量越大，機械性質越優異。因此，為了獲得實用性優異之強度的聚合物，需要為一定程度的高分子量。在本發明中，所使用之酸酐（a1’）與二胺（a2’）與雙胺基苯酚（a3’）的當量比並無特別限制，二胺（a2’）及雙胺基苯酚（a3’）與酸酐（a1’）的當量比在0.70～1.30的範圍為較佳。只要該當量比在上述範圍內，則機械強度優異且製造穩定性優異。The equivalent ratio of acid anhydride (a1') to diamine (a2') to bisaminophenol (a3') in the imidization reaction of step 1 is an important factor determining the molecular weight of the obtained polymer. In general, it is widely known that there is a correlation between the molecular weight of a polymer and the mechanical properties, and the larger the molecular weight, the better the mechanical properties. Therefore, in order to obtain a polymer having a strength excellent in practical use, a certain degree of high molecular weight is required. In the present invention, the equivalent ratio of acid anhydride (a1') to diamine (a2') to bisaminophenol (a3') is not particularly limited. Diamine (a2') and bisaminophenol (a3 ') to the acid anhydride (a1') is preferably in the range of 0.70 to 1.30. As long as the equivalent ratio is within the above range, the mechanical strength is excellent and the production stability is excellent.
再者，就改善機械特性之觀點而言，即使在二胺（a2’）及雙胺基苯酚（a3’）之相對於酸酐（a1’）的當量比脫離上述範圍之情況，亦能夠藉由使樹脂側鏈交聯來提高表觀的分子量。 步驟1（醯亞胺化反應步驟）能夠藉由公知的方法在有機溶劑中進行。 Furthermore, from the viewpoint of improving the mechanical properties, even when the equivalent ratio of the diamine (a2') and the bisaminophenol (a3') to the acid anhydride (a1') deviates from the above-mentioned range, it can be obtained by Cross-linking the resin side chains increases the apparent molecular weight. Step 1 (imidation reaction step) can be performed in an organic solvent by a known method.
作為有機溶劑，可以舉出γ-丁內酯（GBL）、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、四氫呋喃、二乙二醇二甲醚、二乙二醇二***、環己酮、1,4-二㗁烷等非質子性極性溶劑類，可以使用1種或組合使用2種以上。此時，可以混合使用與上述非質子性極性溶劑具有相溶性之非極性溶劑。作為非極性溶劑，可以舉出甲苯、乙苯、二甲苯、對稱三甲苯、溶劑油等芳香族烴類或環戊基甲醚等醚系溶劑等。關於混合溶劑中之非極性溶劑的比例，只要在溶劑的溶解度降低且反應而獲得之聚醯胺酸樹脂不析出的範圍，則能夠依據攪拌裝置能力或溶液黏度等樹脂性狀任意設定。Examples of organic solvents include γ-butyrolactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diglyme, diethyl Aprotic polar solvents such as glycol diethyl ether, cyclohexanone, and 1,4-dioxane can be used alone or in combination of two or more. In this case, a non-polar solvent having compatibility with the above-mentioned aprotic polar solvent may be mixed and used. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, trimethylbenzene, mineral spirits, and ether solvents such as cyclopentyl methyl ether. The ratio of the non-polar solvent in the mixed solvent can be set arbitrarily according to the properties of the resin, such as the ability of the stirring device or the viscosity of the solution, as long as the solubility of the solvent is reduced and the polyamic acid resin obtained by the reaction does not precipitate.
關於反應溫度，在0℃以上且100℃以下，較佳為在20℃以上且80℃以下反應30分鐘～2小時左右之後，在100℃以上且250℃以下，較佳為在120℃以上且200℃以下反應1～5小時左右。The reaction temperature is between 0°C and 100°C, preferably between 20°C and 80°C for about 30 minutes to 2 hours, and then between 100°C and 250°C, preferably between 120°C and 2 hours. React below 200°C for about 1 to 5 hours.
藉由步驟1，能夠獲得具有下述通式（1）所表示之結構單元及下述通式（2’）所表示之結構單元之聚羥基醯亞胺或具有下述通式（3’）所表示之結構單元之聚羥基醯亞胺。再者，在步驟1中，能夠藉由公知的方法純化聚羥基醯亞胺，然而，能夠在提高聚合時的脫水效率且不純化所獲得之聚羥基醯亞胺的情況連續進行步驟1及步驟2。By step 1, a polyhydroxyimide having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2') or having the following general formula (3') can be obtained The structural unit represented is polyhydroxyimide. Furthermore, in Step 1, the polyhydroxyimide can be purified by a known method, however, it is possible to continuously perform Step 1 and Step 1 without purifying the obtained polyhydroxyimide while increasing the dehydration efficiency during polymerization. 2.
該等通式中，R 1～R 4、X 1與通式（a2）的含義相同，X 2與通式（a3）的含義相同，Y與通式（a1）的含義相同，較佳為選自前述通式（a1-1）、（a1-2）或（a1-3）所表示之基。 在步驟2中，使具備（甲基）丙烯酸酯基之化合物與在步驟1中所獲得之聚羥基醯亞胺的羥基進行反應而導入包含（甲基）丙烯酸酯基之交聯基。 導入到聚醯亞胺（A）中之交聯基在曝光步驟中與後述交聯劑（B）進行反應，曝光部變得不溶於有機溶劑中。 In these general formulas, R 1 ~ R 4 , X 1 have the same meaning as the general formula (a2), X 2 has the same meaning as the general formula (a3), Y has the same meaning as the general formula (a1), preferably It is selected from the group represented by the aforementioned general formula (a1-1), (a1-2) or (a1-3). In step 2, a compound having a (meth)acrylate group is reacted with the hydroxyl group of the polyhydroxyimide obtained in step 1 to introduce a crosslinking group including a (meth)acrylate group. The crosslinking group introduced into the polyimide (A) reacts with the crosslinking agent (B) described later in the exposure step, and the exposed part becomes insoluble in the organic solvent.
作為具備（甲基）丙烯酸酯基之化合物，可以舉出（甲基）丙烯酸2-異氰酸基乙酯、2-（2-（甲基）丙烯醯氧基乙基氧基）乙基異氰酸酯、1,1-（雙丙烯醯氧基甲基）乙基異氰酸酯、甲基丙烯酸環氧丙酯、4-羥基丁基丙烯酸酯環氧丙基醚等。Examples of compounds having a (meth)acrylate group include 2-isocyanatoethyl (meth)acrylate, 2-(2-(meth)acryloxyethyloxy)ethylisocyanate , 1,1-(bisacryloxymethyl)ethyl isocyanate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, etc.
為了在聚羥基醯亞胺中導入包含（甲基）丙烯酸酯基之交聯基，在有機溶劑中混合聚羥基醯亞胺和具備（甲基）丙烯酸酯基之化合物，並且在60℃～150℃反應2～10小時左右。反應並無特別限定，能夠在常壓下進行。In order to introduce a cross-linking group containing a (meth)acrylate group into polyhydroxyimide, mix polyhydroxyimide and a compound having a (meth)acrylate group in an organic solvent, and ℃ for about 2 to 10 hours. The reaction is not particularly limited, and can be performed under normal pressure.
關於具備（甲基）丙烯酸酯基之化合物，能夠依據對聚羥基醯亞胺之交聯基的導入量適當選擇，例如能夠以相對於聚羥基醯亞胺的羥基莫耳量成為0.8～3.0莫耳倍的方式添加，2.0～3.0莫耳倍為較佳。再者，在聚羥基醯亞胺具有能夠導入交聯基之基之情況，能夠將該基添加到莫耳量中。The compound having a (meth)acrylate group can be appropriately selected depending on the amount of crosslinking groups introduced into the polyhydroxyimide, for example, the molar amount of hydroxyl groups relative to the polyhydroxyimide can be 0.8 to 3.0 moles Add in the form of mole times, preferably 2.0-3.0 mole times. Furthermore, when the polyhydroxyimide has a group capable of introducing a crosslinking group, the group can be added to the molar amount.
作為有機溶劑，可以舉出γ-丁內酯（GBL）、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、四氫呋喃、二乙二醇二甲醚、二乙二醇二***、環己酮、1,4-二㗁烷等非質子性極性溶劑類，可以使用1種或組合使用2種以上。此時，可以混合使用與上述非質子性極性溶劑具有相溶性之非極性溶劑。作為非極性溶劑，可以舉出甲苯、乙苯、二甲苯、對稱三甲苯、溶劑油等芳香族烴類、環戊基甲醚等醚系溶劑等。 在進行反應時，亦能夠添加三乙胺、1,1,3,3-四甲基胍等鹽基。 Examples of organic solvents include γ-butyrolactone (GBL), N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, diglyme, diethyl Aprotic polar solvents such as glycol diethyl ether, cyclohexanone, and 1,4-dioxane can be used alone or in combination of two or more. In this case, a non-polar solvent having compatibility with the above-mentioned aprotic polar solvent may be mixed and used. Examples of the nonpolar solvent include aromatic hydrocarbons such as toluene, ethylbenzene, xylene, trimethylbenzene and mineral spirits, ether solvents such as cyclopentyl methyl ether, and the like. During the reaction, salt groups such as triethylamine and 1,1,3,3-tetramethylguanidine can also be added.
藉由步驟2，能夠獲得具有通式（1）所表示之結構單元及通式（2）所表示之結構單元之聚醯亞胺（A）或具有通式（3）所表示之結構單元之聚醯亞胺（A）。By step 2, the polyimide (A) having the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) or the polyimide (A) having the structural unit represented by the general formula (3) can be obtained Polyimide (A).
在步驟2中，能夠藉由再沉澱等純化包含在步驟1中所獲得之聚羥基醯亞胺之反應溶液，並使用所獲得之聚羥基醯亞胺，然而，亦能夠將步驟1的反應溶液直接用於步驟2中。In step 2, the reaction solution containing the polyhydroxyimide obtained in step 1 can be purified by reprecipitation or the like, and the obtained polyhydroxyimide can be used, however, the reaction solution of step 1 can also be used directly in step 2.
藉由以上的本實施形態之製造方法，能夠獲得包含本實施形態的聚醯亞胺（A）（負型感光性聚合物）之反應溶液，進而能夠依據需要用有機溶劑等進行稀釋，並將其用作聚合物溶液（塗布用清漆）。作為有機溶劑，能夠使用在反應步驟中所例示者，可以為與反應步驟相同的有機溶劑，亦可以為不同之有機溶劑。According to the production method of the present embodiment above, the reaction solution containing the polyimide (A) (negative photosensitive polymer) of the present embodiment can be obtained, and further diluted with an organic solvent or the like as necessary, and the It is used as a polymer solution (varnish for coating). As an organic solvent, what was exemplified in the reaction step can be used, and it may be the same organic solvent as the reaction step, and may be a different organic solvent.
又，亦能夠將該反應溶液投入到不良溶劑中以使聚醯亞胺（A）樹脂再沉澱析出來去除未反應單體，並將乾燥固化者再度溶解於有機溶劑中，並用作精製產物。尤其在雜質或異物成為問題之用途中，再度溶解於有機溶劑中並過濾純化以製成清漆為較佳。In addition, the reaction solution can also be put into a poor solvent to reprecipitate the polyimide (A) resin to remove unreacted monomers, and the solidified product can be redissolved in an organic solvent and used as a refined product. Especially in applications where impurities or foreign substances are a problem, it is preferable to redissolve in an organic solvent and purify by filtration to obtain a varnish.
（第2實施形態） 本實施形態的聚醯亞胺（A）包含前述通式（a1）所表示之結構單元（a1）和前述通式（a2）所表示之結構單元（a2），其兩個末端中的至少一者為（甲基）丙烯酸酯基。 (Second Embodiment) The polyimide (A) of this embodiment comprises the structural unit (a1) represented by the aforementioned general formula (a1) and the structural unit (a2) represented by the aforementioned general formula (a2), at least one of its two ends Those are (meth)acrylate groups.
在本實施形態中，聚醯亞胺（A）的兩個末端中的至少一者為（甲基）丙烯酸酯基。藉由包含該基，伸長率等機械強度優異。 能夠藉由 1H-NMR來分析出具有（甲基）丙烯酸酯基。 具體而言，聚醯亞胺（A）在兩個末端中的至少一者具備前述通式（a4）所表示之末端結構（a4）或前述通式（a5）所表示之末端結構（a5）中的至少1個為較佳，具備末端結構（a4）為較佳。 In this embodiment, at least one of both terminals of the polyimide (A) is a (meth)acrylate group. By including this group, mechanical strength such as elongation is excellent. It can be analyzed by 1 H-NMR that it has a (meth)acrylate group. Specifically, at least one of the two terminals of the polyimide (A) has the terminal structure (a4) represented by the aforementioned general formula (a4) or the terminal structure (a5) represented by the aforementioned general formula (a5) At least one of them is preferred, and it is preferred to have a terminal structure (a4).
具體而言，本實施形態的聚醯亞胺（A）包含下述通式（1）所表示之結構單元為較佳。Specifically, it is preferable that the polyimide (A) of the present embodiment includes a structural unit represented by the following general formula (1).
本實施形態的聚醯亞胺（A）的重量平均分子量為5,000～200,000，較佳為10,000～100,000。The weight average molecular weight of the polyimide (A) of this embodiment is 5,000-200,000, Preferably it is 10,000-100,000.
本實施形態的聚醯亞胺（A）的水解得到抑制，聚醯亞胺（A）及包含聚醯亞胺（A）之負型感光性樹脂組成物能夠獲得伸長率等機械強度優異之膜等硬化物。 又，本實施形態的聚醯亞胺（A）對溶劑的溶解性優異，且無需在前驅物的狀態下製成清漆，因此能夠製備包含聚醯亞胺（A）之清漆，從而能夠由該清漆獲得膜等硬化物。 The hydrolysis of the polyimide (A) of this embodiment is suppressed, and the polyimide (A) and the negative photosensitive resin composition containing the polyimide (A) can obtain a film excellent in mechanical strength such as elongation Wait for hardening. In addition, the polyimide (A) of this embodiment has excellent solubility in solvents, and it is not necessary to prepare a varnish in the state of a precursor, so it is possible to prepare a varnish containing the polyimide (A), and it is possible to use this The varnish obtains a hardened product such as a film.
＜聚醯亞胺（A）之製造方法＞ 本實施形態的聚醯亞胺（A）除了不使用前述通式（a3’）所表示之雙胺基苯酚（a3’）以外，能夠藉由與第1實施形態相同的方法進行。 ＜Method for producing polyimide (A)＞ The polyimide (A) of this embodiment can be produced by the same method as that of the first embodiment except that the bisaminophenol (a3') represented by the aforementioned general formula (a3') is not used.
再者，在本實施形態中，所使用之酸酐（a1’）與二胺（a2’）的當量比並無特別限制，二胺（a2’）與酸酐（a1’）的當量比在0.70～1.30的範圍為較佳。在未達0.70時，分子量低而變脆，因此機械強度變弱。又，若超過1.30，則分子量低而變脆，因此機械強度變弱。亦即，只要該當量比在上述範圍，則機械強度優異且製造穩定性優異。Furthermore, in this embodiment, the equivalent ratio of the acid anhydride (a1') to the diamine (a2') is not particularly limited, and the equivalent ratio of the diamine (a2') to the acid anhydride (a1') is between 0.70 and The range of 1.30 is better. When it is less than 0.70, the molecular weight is low and becomes brittle, so the mechanical strength becomes weak. Moreover, when exceeding 1.30, since molecular weight will become low and will become brittle, mechanical strength will become weak. That is, as long as the equivalent ratio is in the above-mentioned range, the mechanical strength is excellent and the production stability is excellent.
本實施形態的聚醯亞胺（A）（負型感光性聚合物）的耐水解性優異，在以下條件測得之重量平均分子量的減少率為15%以下，較佳為12%以下。 條件為下： 在前述負型感光性聚合物100質量份中添加γ-丁內酯400質量份、4-甲基四氫吡喃200質量份及水50質量份並在100℃攪拌了6小時之情況，藉由下述公式進行計算。 公式：[（試驗前的重量平均分子量-試驗後的重量平均分子量）/試驗前的重量平均分子量]×100 The polyimide (A) (negative photosensitive polymer) of this embodiment has excellent hydrolysis resistance, and the reduction rate of the weight average molecular weight measured under the following conditions is 15% or less, preferably 12% or less. The conditions are as follows: 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of the aforementioned negative photosensitive polymer and stirred at 100°C for 6 hours. Calculated by the following formula. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100
藉由本實施形態的負型感光性聚合物的重量平均分子量的減少率在上述範圍，能夠獲得伸長率等機械強度優異之膜等硬化物。When the reduction rate of the weight average molecular weight of the negative photosensitive polymer of this embodiment exists in the said range, hardened|cured products, such as a film excellent in mechanical strength, such as elongation, can be obtained.
將本實施形態的負型感光性聚合物的較佳摻合例示於以下表1中。The preferable compounding example of the negative photosensitive polymer of this embodiment is shown in following Table 1.
[表1]
·MED-J：4,4-二胺基-3,3-二乙基-5,5-二甲基二苯基甲烷 ·HFBAPP：4,4’-（六氟亞異丙基）雙[（4-胺基苯氧基）苯] ·BAPA：2,2-雙（3-胺基-4-羥基苯基）丙烷 ·BAFA：2,2-雙（3-胺基-4-羥基苯基）六氟丙烷 ·TMPBP-TME：4-[4-（1,3-二氧代異苯并呋喃（dioxoisobenzofuran）-5-基羰氧基）-2,3,5-三甲基苯基]-2,3,6-三甲基苯基1,3-二氧代異苯并呋喃-5-羧酸酯 ·TMHQ：對伸苯基雙（偏苯三酸酐（trimellitate anhydride）） ·AOI：丙烯酸2-異氰酸基乙酯 ·MOI：甲基丙烯酸2-異氰酸基乙酯 MED-J: 4,4-diamino-3,3-diethyl-5,5-dimethyldiphenylmethane HFBAPP: 4,4'-(hexafluoroisopropylidene)bis[(4-aminophenoxy)benzene] BAPA: 2,2-bis(3-amino-4-hydroxyphenyl)propane BAFA: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane TMPBP-TME: 4-[4-(1,3-dioxoisobenzofuran-5-ylcarbonyloxy)-2,3,5-trimethylphenyl]-2,3 ,6-Trimethylphenyl 1,3-dioxoisobenzofuran-5-carboxylate TMHQ: p-phenylene bis(trimellitate anhydride) AOI: 2-isocyanatoethyl acrylate MOI: 2-isocyanatoethyl methacrylate
[交聯劑（B）] 交聯劑（B）包含多官能（甲基）丙烯酸酯。 前述多官能（甲基）丙烯酸酯為具有2個以上的（甲基）丙烯醯基之化合物，只要能夠發揮本發明的效果，則能夠使用以往公知的化合物。再者，在本實施形態中，（甲基）丙烯酸基表示丙烯酸基或甲基丙烯酸基。 [Crosslinking agent (B)] The crosslinking agent (B) contains polyfunctional (meth)acrylate. The polyfunctional (meth)acrylate is a compound having two or more (meth)acryl groups, and conventionally known compounds can be used as long as the effect of the present invention can be exhibited. In addition, in this embodiment, a (meth)acryl group represents an acryl group or a methacryl group.
作為具體的多官能（甲基）丙烯酸酯，可以舉出二乙二醇二（甲基）丙烯酸酯、聚乙二醇#200二（甲基）丙烯酸酯、聚乙二醇#400二（甲基）丙烯酸酯等二官能（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、乙氧基化異三聚氰酸三丙烯酸酯等三官能（甲基）丙烯酸酯、新戊四醇四（甲基）丙烯酸酯、二三羥甲基丙烷四（甲基）丙烯酸酯等四官能（甲基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯等六官能（甲基）丙烯酸酯、三新戊四醇八（甲基）丙烯酸酯等八官能（甲基）丙烯酸酯、四新戊四醇十（甲基）丙烯酸酯等十官能（甲基）丙烯酸酯。該等之中，可以使用1種或2種以上。Specific examples of polyfunctional (meth)acrylates include diethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #400 di(meth)acrylate, and polyethylene glycol #400 di(meth)acrylate. Difunctional (meth)acrylate such as acrylate, trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate, ethoxylated isocyanuric acid triacrylic acid Trifunctional (meth)acrylates such as esters, tetrafunctional (meth)acrylates such as neopentylthritol tetra(meth)acrylates, ditrimethylolpropane tetra(meth)acrylates, dineopentyl tetra(meth)acrylates, Hexafunctional (meth)acrylates such as alcohol hexa(meth)acrylates, octafunctional (meth)acrylates such as trineopentaerythritol octa(meth)acrylates, tetraneopenylthritol deca(meth)acrylates Decafunctional (meth)acrylates such as acrylates. Among these, 1 type or 2 or more types can be used.
就本發明的效果的觀點而言，相對於聚醯亞胺（A）100質量份之交聯劑（B）的量能夠設為1質量份以上且30質量份以下，較佳為2質量份以上且20質量份以下，較佳為3質量份以上且15質量份以下。藉由在該範圍，能夠進一步改善伸長率。From the viewpoint of the effects of the present invention, the amount of the crosslinking agent (B) can be 1 to 30 parts by mass, preferably 2 parts by mass, relative to 100 parts by mass of the polyimide (A). It is more than 20 mass parts, Preferably it is 3 mass parts or more and 15 mass parts or less. By being in this range, elongation can be further improved.
[光聚合起始劑（C）] 作為光聚合起始劑（C），例如能夠使用光自由基產生劑。作為光自由基產生劑，含有藉由紫外線等活性光線的照射而產生自由基以作為上述聚醯亞胺（A）的光聚合起始劑而發揮作用之光自由基產生劑。 [Photopolymerization initiator (C)] As a photoinitiator (C), a photoradical generator can be used, for example. As a photoradical generator, the photoradical generator which generate|occur|produces a radical by irradiation of active light rays, such as an ultraviolet-ray, and functions as a photopolymerization initiator of the said polyimide (A) is contained.
作為前述光自由基產生劑，可以舉出烷基苯基酮型起始劑、肟酯型起始劑、醯基膦氧化物型起始劑等。例如，可以舉出1-羥基環己基苯基酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮、2-甲基-1- [4-（甲基硫基）苯基]-2-
聚合起始劑（C）的添加量並無特別限定，負型感光性樹脂組成物的除了溶劑以外的非揮發性成分100質量%的0.3～20質量%左右為較佳，0.5～15質量%左右為更佳，1～10質量%左右為進而較佳。藉由將聚合起始劑（C）的添加量設定在前述範圍內，能夠提高包含負型感光性樹脂組成物之感光性樹脂層的圖案形成性，並且能夠提高負型感光性樹脂組成物的長期保管性。The addition amount of the polymerization initiator (C) is not particularly limited, but about 0.3 to 20% by mass of 100% by mass of the non-volatile components other than the solvent in the negative photosensitive resin composition is preferably about 0.5 to 15% by mass. About more is more preferable, and about 1 to 10 mass % is still more preferable. By setting the addition amount of the polymerization initiator (C) within the aforementioned range, the pattern formability of the photosensitive resin layer including the negative photosensitive resin composition can be improved, and the photosensitive resin composition of the negative photosensitive resin composition can be improved. Long-term storage.
（溶劑） 本實施形態之負型感光性樹脂組成物能夠包含溶劑。藉此，能夠在各種基板表面形成均勻的感光性樹脂膜。 (solvent) The negative photosensitive resin composition of this embodiment can contain a solvent. Thereby, a uniform photosensitive resin film can be formed on the surfaces of various substrates.
作為溶劑，可以較佳地使用有機溶劑。具體而言，能夠使用酮系溶劑、酯系溶劑、醚系溶劑、醇系溶劑、內酯系溶劑、碳酸酯系溶劑等中的1種或2種以上。As the solvent, an organic solvent can be preferably used. Specifically, one or two or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, and the like can be used.
作為溶劑的例，可以舉出丙二醇單甲醚（PGME）、丙二醇單甲醚乙酸酯（PGMEA）、乳酸乙酯、甲基異丁基甲醇（MIBC）、γ-丁內酯（GBL）、N-甲基吡咯啶酮（NMP）、甲基正戊酮（MAK）、二乙二醇單甲醚、二乙二醇二甲醚、二乙二醇甲基***、環己酮或該等混合物。 溶劑的使用量並無特別限定。例如，以非揮發性成分的濃度例如成為10～70質量%，較佳為成為15～60質量%的量進行使用。 Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), γ-butyrolactone (GBL), N-Methylpyrrolidone (NMP), Methyl Pentanone (MAK), Diethylene Glycol Monomethyl Ether, Diethylene Glycol Dimethyl Ether, Diethylene Glycol Methyl Ether, Cyclohexanone or the like mixture. The usage-amount of a solvent is not specifically limited. For example, the concentration of the non-volatile components is used in an amount of, for example, 10 to 70% by mass, preferably 15 to 60% by mass.
（界面活性劑） 本實施形態之負型感光性樹脂組成物可以進一步包含界面活性劑。 作為界面活性劑，並無限定，具體而言，可以舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類；聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等聚氧乙烯芳基醚類；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等聚氧乙烯二烷基酯類等非離子系界面活性劑；用F-TOP EF301、F-TOP EF303、F-TOP EF352（Shin-Akita Chemical Co., Ltd.製）、MEGAFACE F171、MEGAFACE F172、MEGAFACE F173、MEGAFACE F177、MEGAFACE F444、MEGAFACE F470、MEGAFACE F471、MEGAFACE F475、MEGAFACE F482、MEGAFACE F477（DIC CORPORATION製）、Fluorad FC-430、Fluorad FC-431、Novell FC4430、Novell FC4432（3M Japan Limited製）、Surflon S-381、Surflon S-382、Surflon S-383、Surflon S-393、Surflon SC-101、Surflon SC-102、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-106、（AGC SEIMI CHEMICAL CO., LTD.製）等名稱市售之氟系界面活性劑；有機矽氧烷共聚物KP341（Shin-Etsu Chemical Co., Ltd.製）；（甲基）丙烯酸系共聚物Polyflow No.57、95（Kyoeisha chemical Co.,Ltd.製）等。 (surfactant) The negative photosensitive resin composition of this embodiment may further contain a surfactant. The surfactant is not limited, but specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.; polyoxyethylene octane Polyoxyethylene aryl ethers such as phenyl phenyl ether and polyoxyethylene nonylphenyl ether; nonionic polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate Surfactant; use F-TOP EF301, F-TOP EF303, F-TOP EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MEGAFACE F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F177, MEGAFACE F444, MEGAFACE F470 , MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC CORPORATION), Fluorad FC-430, Fluorad FC-431, Novell FC4430, Novell FC4432 (manufactured by 3M Japan Limited), Surflon S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, (manufactured by AGC SEIMI CHEMICAL CO., LTD. ) and other commercially available fluorine-based surfactants; organosiloxane copolymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth)acrylic copolymer Polyflow No.57, 95 (Kyoeisha Chemical Co. ., Ltd.), etc.
該等之中，使用具有全氟烷基之氟系界面活性劑為較佳。作為具有全氟烷基之氟系界面活性劑，使用選自上述具體例中的MEGAFACE F171、MEGAFACE F173、MEGAFACE F444、MEGAFACE F470、MEGAFACE F471、MEGAFACE F475、MEGAFACE F482、MEGAFACE F477（DIC CORPORATION製）、Surflon S-381、Surflon S-383、Surflon S-393（AGC SEIMI CHEMICAL CO., LTD.製）、Novell FC4430及Novell FC4432（3M Japan Limited製）中之1種或2種以上為較佳。Among them, it is preferable to use a fluorine-based surfactant having a perfluoroalkyl group. As the fluorine-based surfactant having a perfluoroalkyl group, MEGAFACE F171, MEGAFACE F173, MEGAFACE F444, MEGAFACE F470, MEGAFACE F471, MEGAFACE F475, MEGAFACE F482, MEGAFACE F477 (manufactured by DIC CORPORATION), One or more of Surflon S-381, Surflon S-383, Surflon S-393 (manufactured by AGC SEIMI CHEMICAL CO., LTD.), Novell FC4430 and Novell FC4432 (manufactured by 3M Japan Limited) are preferred.
又，作為界面活性劑，亦能夠較佳地使用聚矽氧系界面活性劑（例如聚醚改質二甲基矽氧烷等）。作為聚矽氧系界面活性劑，具體而言，可以舉出Dow Toray Co.,Ltd.的SH系列、SD系列及ST系列、BYK JAPAN KK.的BYK系列、Shin-Etsu Chemical Co., Ltd.的KP系列、NOF CORPORATION的DISFOAM（註冊商標）系列、TOSHIBA CORPORATION的TSF系列等。Moreover, as a surfactant, a polysiloxane-based surfactant (for example, polyether-modified dimethylsiloxane, etc.) can also be preferably used. Specific examples of polysiloxane-based surfactants include SH series, SD series, and ST series from Dow Toray Co., Ltd., BYK series from BYK JAPAN KK., and Shin-Etsu Chemical Co., Ltd. KP series of NOF CORPORATION, DISFOAM (registered trademark) series of NOF CORPORATION, TSF series of TOSHIBA CORPORATION, etc.
負型感光性樹脂組成物中的界面活性劑的含量的上限值相對於負型感光性樹脂組成物的總體（包含溶劑）為1質量%（10000ppm）以下為較佳，0.5質量%（5000ppm）以下為更佳，0.1質量%（1000ppm）以下為進而較佳。The upper limit of the content of the surfactant in the negative photosensitive resin composition is preferably 1% by mass (10000ppm) or less, and 0.5% by mass (5000ppm ) or less is more preferable, and 0.1 mass % (1000 ppm) or less is still more preferable.
又，負型感光性樹脂組成物中的界面活性劑的含量的下限值並無特別限定，但就充分獲得界面活性劑所致之效果之觀點而言，例如相對於負型感光性樹脂組成物的總體（包含溶劑）為0.001質量%（10ppm）以上。 藉由適當調節界面活性劑的量，能夠在維持其他性能的同時，提高塗布性和塗膜的均勻性等。 Also, the lower limit of the content of the surfactant in the negative photosensitive resin composition is not particularly limited, but from the viewpoint of sufficiently obtaining the effect of the surfactant, for example, with respect to the negative photosensitive resin composition The total amount of the substance (including the solvent) is 0.001% by mass (10 ppm) or more. By properly adjusting the amount of the surfactant, it is possible to improve the applicability and the uniformity of the coating film while maintaining other properties.
（抗氧化劑） 本實施形態之負型感光性樹脂組成物可以進一步包含抗氧化劑。作為抗氧化劑，能夠使用選自酚系抗氧化劑、磷系抗氧化劑及硫醚系抗氧化劑之1種以上。抗氧化劑能夠抑制由負型感光性樹脂組成物形成之樹脂膜的氧化。 (Antioxidants) The negative photosensitive resin composition of this embodiment may further contain an antioxidant. As the antioxidant, one or more selected from the group consisting of phenolic antioxidants, phosphorus antioxidants, and thioether antioxidants can be used. An antioxidant can suppress the oxidation of the resin film formed from the negative photosensitive resin composition.
作為酚系抗氧化劑，可以舉出新戊四醇-四〔3-（3,5-二-三級丁基-4-羥基苯基）丙酸酯〕、3,9-雙｛2-〔3-（3-三級丁基-4-羥基-5-甲基苯基）丙醯氧基〕-1,1-二甲基乙基｝2,4,8,10-四氧雜螺〔5,5〕十一烷、十八烷基-3-（3,5-二-三級丁基-4-羥基苯基）丙酸酯、1,6-己二醇-雙〔3-（3,5-二-三級丁基-4-羥基苯基）丙酸酯〕、1,3,5-三甲基-2,4,6-三（3,5-二-三級丁基-4-羥基苄基）苯、2,6-二-三級丁基-4-甲基苯酚、2,6-二-三級丁基-4-乙基苯酚、2,6-二苯基-4-十八烷氧基苯酚、硬脂基（3,5-二-三級丁基-4-羥基苯基）丙酸酯、二硬脂基（3,5-二-三級丁基-4-羥基苄基）膦酸酯、硫二乙二醇雙〔（3,5-二-三級丁基-4-羥基苯基）丙酸酯〕、4,4’-硫代雙（6-三級丁基-間甲酚）、2-辛硫基-4,6-二（3,5-二-三級丁基-4-羥基苯氧基）-對稱三𠯤、2,2’-亞甲基雙（4-甲基-6-三級丁基-6-丁基苯酚）、2,2’-亞甲基雙（4-乙基-6-三級丁基苯酚）、雙〔3,3-雙（4-羥基-3-三級丁基苯基）丁酸〕醇酯、4,4’-亞丁基雙（6-三級丁基-間甲酚）、2,2’-亞乙基雙（4,6-二-三級丁基苯酚）、2,2’-亞乙基雙（4-二級丁基-6-三級丁基苯酚）、1,1,3-三（2-甲基-4-羥基-5-三級丁基苯基）丁烷、雙〔2-三級丁基-4-甲基-6-（2-羥基-3-三級丁基-5-甲基苄基）苯基〕對酞酸酯、1,3,5-三（2,6-二甲基-3-羥基-4-三級丁基苄基）異氰酸酯、1,3,5-三（3,5-二-三級丁基-4-羥基苄基）-2,4,6-三甲基苯、1,3,5-三〔（3,5-二-三級丁基-4-羥基苯基）丙醯氧基乙基〕異氰酸酯、四〔亞甲基-3-（3,5-二-三級丁基-4-羥基苯基）丙酸酯〕甲烷、2-三級丁基-4-甲基-6-（2-丙烯醯氧基-3-三級丁基-5-甲基苄基）苯酚、3,9-雙（1,1-二甲基-2-羥乙基）-2,4-8,10-四氧雜螺[5,5]十一烷-雙〔β-（3-三級丁基-4-羥基-5-甲基苯基）丙酸酯〕、三乙二醇雙〔β-（3-三級丁基-4-羥基-5-甲基苯基）丙酸酯〕、1,1’-雙（4-羥基苯基）環己烷、2,2’-亞甲基雙（4-甲基-6-三級丁基苯酚）、2,2’-亞甲基雙（4-乙基-6-三級丁基苯酚）、2,2’-亞甲基雙（6-（1-甲基環己基）-4-甲基苯酚）、4,4’-亞丁基雙（3-甲基-6-三級丁基苯酚）、3,9-雙（2-（3-三級丁基-4-羥基-5-甲基苯基丙醯氧基）1,1-二甲基乙基）-2,4,8,10-四氧雜螺（5,5）十一烷、4,4’-硫代雙（3-甲基-6-三級丁基苯酚）、4,4’-雙（3,5-二-三級丁基-4-羥基苄基）硫醚、4,4’-硫代雙（6-三級丁基-2-甲基苯酚）、2,5-二-三級丁基氫醌、2,5-二-三級戊基氫醌、2-三級丁基-6-（3-三級丁基-2-羥基-5-甲基苄基）-4-甲基苯基丙烯酸酯、2,4-二甲基-6-（1-甲基環己基、苯乙烯基苯酚、2,4-雙（（辛硫基）甲基）-5-甲基苯酚等。Examples of phenolic antioxidants include neopentylthritol-tetrakis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 3,9-bis{2-[ 3-(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[ 5,5) undecane, octadecyl-3-(3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis[3-( 3,5-di-tertiary butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tertiary butyl -4-hydroxybenzyl)benzene, 2,6-di-tertiary butyl-4-methylphenol, 2,6-di-tertiary butyl-4-ethylphenol, 2,6-diphenyl -4-octadecyloxyphenol, stearyl (3,5-di-tertiary butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tertiary butyl -4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis( 6-tertiary butyl-m-cresol), 2-octylthio-4,6-bis(3,5-di-tertiary butyl-4-hydroxyphenoxy)-symmetrical trioxyl, 2,2 '-Methylenebis(4-methyl-6-tert-butyl-6-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), Bis[3,3-bis(4-hydroxy-3-tertiary butylphenyl)butanoic acid] alcohol ester, 4,4'-butylene bis(6-tertiary butyl-m-cresol), 2, 2'-Ethylenebis(4,6-di-tertiary butylphenol), 2,2'-ethylenebis(4-secondary butyl-6-tertiary butylphenol), 1,1 ,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, bis[2-tertiary butyl-4-methyl-6-(2-hydroxy-3-tri butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tertiary butylbenzyl)isocyanate, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5- Di-tertiary butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanate, tetrakis[methylene-3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionic acid Ester] methane, 2-tertiary butyl-4-methyl-6-(2-acryloyloxy-3-tertiary butyl-5-methylbenzyl)phenol, 3,9-bis(1, 1-Dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5]undecane-bis[β-(3-tertiary butyl-4-hydroxy- 5-methylphenyl)propionate], triethylene glycol bis[β-(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis (4-hydroxyphenyl)cyclohexane, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl- 6-tertiary butylphenol), 2,2'-methylenebis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylenebis(3-methyl -6-tertiary butylphenol), 3,9-bis(2-(3-tertiary butyl-4-hydroxy-5-methylphenylpropionyloxy) 1,1-dimethylethyl )-2,4,8,10-tetraoxaspiro(5,5)undecane, 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4' -bis(3,5-di-tertiary butyl-4-hydroxybenzyl)sulfide, 4,4'-thiobis(6-tertiary butyl-2-methylphenol), 2,5- Di-tertiary butyl hydroquinone, 2,5-di-tertiary pentyl hydroquinone, 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-dimethyl-6-(1-methylcyclohexyl, styrylphenol, 2,4-bis((octylthio)methyl)-5- methyl phenol etc.
作為磷系抗氧化劑，可以舉出雙（2,6-二-三級丁基-4-甲基苯基）新戊四醇二亞磷酸酯、三（2,4-二-三級丁基苯基亞磷酸酯）、四（2,4-二-三級丁基-5-甲基苯基）-4,4’-聯伸苯基二亞膦酸酯、3,5-二-三級丁基-4-羥基苄基膦酸酯-二乙基酯、雙-（2,6-二異丙苯基苯基）新戊四醇二亞磷酸酯、2,2-亞甲基雙（4,6-二-三級丁基苯基）辛基亞磷酸酯、三（混合單及二-壬基苯基）亞磷酸酯、雙（2,4-二-三級丁基苯基）新戊四醇二亞磷酸酯、雙（2,6-二-三級丁基-4-甲氧基羰基乙基-苯基）新戊四醇二亞磷酸酯、雙（2,6-二-三級丁基-4-十八烷氧基羰基乙基苯基）新戊四醇二亞磷酸酯等。Examples of phosphorus antioxidants include bis(2,6-di-tertiary butyl-4-methylphenyl) neopentylitol diphosphite, tris(2,4-di-tertiary butyl phenyl phosphite), tetrakis(2,4-di-tertiary butyl-5-methylphenyl)-4,4'-biphenylene diphosphonite, 3,5-di-tri Butyl-4-hydroxybenzylphosphonate-diethyl ester, bis-(2,6-dicumylphenyl) neopentylthritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl)octyl phosphite, tris(mixed mono- and di-nonylphenyl)phosphite, bis(2,4-di-tert-butylphenyl) ) neopentylthritol diphosphite, bis(2,6-di-tertiary butyl-4-methoxycarbonylethyl-phenyl) neopentylthritol diphosphite, bis(2,6- Di-tertiary butyl-4-octadecyloxycarbonylethylphenyl) neopentylthritol diphosphite, etc.
作為硫醚系抗氧化劑，可以舉出二月桂基-3,3’-硫代二丙酸酯、雙（2-甲基-4-（3-正十二烷基）硫代丙醯氧基）-5-三級丁基苯基）硫醚、二硬脂基-3,3’-硫代二丙酸酯、新戊四醇-四（3-月桂基）硫代丙酸酯等。Examples of thioether-based antioxidants include dilauryl-3,3'-thiodipropionate, bis(2-methyl-4-(3-n-dodecyl)thiopropionyloxy )-5-tertiary butylphenyl) sulfide, distearyl-3,3'-thiodipropionate, neopentylthritol-tetra(3-lauryl)thiopropionate, etc.
（密接助劑） 本實施形態之負型感光性樹脂組成物可以進一步包含密接助劑。 作為密接助劑，例如能夠使用胺基矽烷、環氧矽烷、（甲基）丙烯酸矽烷、巰基矽烷、乙烯基矽烷、脲基矽烷、酸酐官能型矽烷、硫化物矽烷等矽烷偶合劑。矽烷偶合劑可以單獨使用1種，亦可以同時使用2種以上。該等之中，環氧矽烷（亦即，在1分子中包含環氧部位和藉由水解而產生矽烷醇基之基這兩者之化合物）或酸酐官能型矽烷（亦即，在1分子中包含酸酐基和藉由水解而產生矽烷醇基之基這兩者之化合物）為較佳。 (adhesion aid) The negative photosensitive resin composition of this embodiment may further contain an adhesion assistant. As the adhesion aid, for example, silane coupling agents such as aminosilane, epoxysilane, (meth)acrylsilane, mercaptosilane, vinylsilane, ureidosilane, anhydride functional silane, and sulfide silane can be used. A silane coupling agent may be used individually by 1 type, and may use 2 or more types together. Among them, epoxysilane (that is, a compound containing both an epoxy site and a silanol group by hydrolysis in one molecule) or an anhydride functional silane (that is, a compound in one molecule A compound containing both an acid anhydride group and a group generating a silanol group by hydrolysis) is preferred.
作為胺基矽烷，例如可以舉出雙（2-羥乙基）-3-胺基丙基三乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、N-β（胺基乙基）γ-胺基丙基三甲氧基矽烷、N-β（胺基乙基）γ-胺基丙基三乙氧基矽烷、N-β（胺基乙基）γ-胺基丙基甲基二甲氧基矽烷、N-β（胺基乙基）γ-胺基丙基甲基二乙氧基矽烷或N-苯基-γ-胺基-丙基三甲氧基矽烷等。Examples of aminosilanes include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-beta (aminoethyl) γ-aminopropyltrimethoxysilane , N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(amine ethyl) γ-aminopropylmethyldiethoxysilane or N-phenyl-γ-amino-propyltrimethoxysilane, etc.
作為環氧矽烷，例如可以舉出γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷或β-（3,4-環氧環己基）乙基三甲氧基矽烷、γ-環氧丙基丙基三甲氧基矽烷等。Examples of epoxysilanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane or β-(3,4-epoxy Hexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, etc.
作為丙烯酸矽烷，例如可以舉出γ-（甲基丙烯醯氧基丙基）三甲氧基矽烷、γ-（甲基丙烯醯氧基丙基）甲基二甲氧基矽烷或γ-（甲基丙烯醯氧基丙基）甲基二乙氧基矽烷等。 作為巰基矽烷，例如可以舉出3-巰基丙基三甲氧基矽烷等。 Examples of acrylic silanes include γ-(methacryloxypropyl)trimethoxysilane, γ-(methacryloxypropyl)methyldimethoxysilane or γ-(methyl Acryloxypropyl) methyldiethoxysilane, etc. As mercaptosilane, 3-mercaptopropyltrimethoxysilane etc. are mentioned, for example.
作為乙烯基矽烷，例如可以舉出乙烯基三（β-甲氧基乙氧基）矽烷、乙烯基三乙氧基矽烷或乙烯基三甲氧基矽烷等。 作為脲基矽烷，例如可以舉出3-脲基丙基三乙氧基矽烷等。 Examples of vinylsilane include vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like. As ureidosilane, 3-ureidopropyltriethoxysilane etc. are mentioned, for example.
作為酸酐官能型矽烷，例如可以舉出Shin-Etsu Chemical Co., Ltd.製的，產品名稱X-12-967C（化合物名稱：3-三甲氧基矽基丙基琥珀酸酐）等。As an acid anhydride functional silane, the product made by Shin-Etsu Chemical Co., Ltd., product name X-12-967C (compound name: 3-trimethoxysilylpropyl succinic anhydride), etc. are mentioned, for example.
作為硫化物矽烷，例如可以舉出雙（3-（三乙氧基矽基）丙基）二硫醚或雙（3-（三乙氧基矽基）丙基）四硫醚等。 密接助劑的添加量並無特別限定，其為負型感光性樹脂組成物的固體成分總體的0.1～5質量%，較佳為0.5～3質量%。 Examples of sulfide silanes include bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, and the like. The addition amount of an adhesion aid is not specifically limited, It is 0.1-5 mass % of the whole solid content of a negative photosensitive resin composition, Preferably it is 0.5-3 mass %.
（負型感光性樹脂組成物的製備） 製備本實施形態中之負型感光性樹脂組成物之方法並無限定，能夠依據負型感光性樹脂組成物中所包含之成分，使用公知的方法。 例如，能夠藉由將上述各成分混合於溶劑中並進行溶解來製備。 (Preparation of negative photosensitive resin composition) The method of preparing the negative photosensitive resin composition in this embodiment is not limited, and a known method can be used depending on the components contained in the negative photosensitive resin composition. For example, it can manufacture by mixing and dissolving each said component in a solvent.
（負型感光性樹脂組成物） 關於本實施形態之負型感光性樹脂組成物，將該負型感光性樹脂組成物塗布於具備Al、Cu等金屬之面，接著藉由進行預烘烤（pre bake）使其乾燥而形成樹脂膜，接著藉由進行曝光及顯影將樹脂膜圖案形成為所需的形狀，接著藉由對樹脂膜進行熱處理使其硬化而形成硬化膜，從而進行使用。 (Negative Photosensitive Resin Composition) Regarding the negative photosensitive resin composition of the present embodiment, the negative photosensitive resin composition is applied to a surface having a metal such as Al, Cu, etc., followed by pre-baking and drying to form a resin. The film is then used by forming a resin film pattern into a desired shape by performing exposure and development, and then curing the resin film by heat treatment to form a cured film.
再者，在製作上述永久膜之情況，作為預烘烤的條件，例如能夠設為在溫度90℃以上且130℃以下進行30秒以上且1小時以下的熱處理。又，作為熱處理的條件，例如能夠設為在溫度150℃以上且250℃以下進行30分鐘以上且10小時以下的熱處理，較佳為能夠在170℃左右進行1～6小時的熱處理。In addition, when producing the said permanent film, as a prebaking condition, it can heat-process at the temperature 90 degreeC or more and 130 degreeC or less, for 30 seconds or more and 1 hour or less, for example. In addition, as the conditions of the heat treatment, for example, the heat treatment can be performed at a temperature of 150°C to 250°C for 30 minutes to 10 hours, preferably at about 170°C for 1 to 6 hours.
關於由本實施形態的負型感光性樹脂組成物獲得之膜，藉由以Tensilon試驗機進行之拉伸試驗而測得之伸長率的最大值為15～200%，較佳為20～150%，平均值為10～150%，較佳為15～120%。Regarding the film obtained from the negative photosensitive resin composition of this embodiment, the maximum value of the elongation measured by the tensile test carried out with a Tensilon testing machine is 15 to 200%, preferably 20 to 150%, The average value is 10 to 150%, preferably 15 to 120%.
關於由本實施形態的負型感光性樹脂組成物獲得之膜，藉由以Tensilon試驗機進行之拉伸試驗而測得之拉伸強度為20MPa以上為較佳，30～300MPa為更佳。The film obtained from the negative photosensitive resin composition of this embodiment preferably has a tensile strength of 20 MPa or more, more preferably 30 to 300 MPa, as measured by a tensile test using a Tensilon testing machine.
又，本實施形態的負型感光性樹脂組成物包含耐水解性優異之聚醯亞胺（A）（負型感光性聚合物），因此即使在溫度130℃、相對濕度85%RH的條件進行96小時的HAST試驗（不飽和加壓蒸氣試驗）之後，下述公式所表示之伸長率（最大值、平均值）的降低率亦為20%以下，較佳為15%以下，進而較佳為12%以下。 [（試驗前的伸長率-試驗後的伸長率）/試驗前的伸長率）]×100 In addition, the negative photosensitive resin composition of this embodiment contains polyimide (A) (negative photosensitive polymer) which is excellent in hydrolysis resistance, so even if the temperature is 130°C, the relative humidity is 85%RH. After 96 hours of HAST test (unsaturated pressurized steam test), the reduction rate of elongation (maximum value, average value) represented by the following formula is also 20% or less, preferably 15% or less, and more preferably Below 12%. [(Elongation before test-Elongation after test)/Elongation before test)]×100
本實施形態的負型感光性樹脂組成物的低溫硬化性優異。 例如，將本實施形態的負型感光性樹脂組成物在170℃硬化4小時而獲得之硬化物的玻璃轉移溫度（Tg）能夠設為200℃以上，較佳為210℃以上，進而較佳為220℃以上。 The negative photosensitive resin composition of this embodiment is excellent in low-temperature curability. For example, the glass transition temperature (Tg) of the cured product obtained by curing the negative photosensitive resin composition of this embodiment at 170°C for 4 hours can be set to 200°C or higher, preferably 210°C or higher, and more preferably Above 220°C.
進而，將本實施形態的負型感光性樹脂組成物在170℃硬化4小時而獲得之硬化物在30℃之儲存彈性模數E’能夠設為2.0GPa以上，較佳為2.5GPa以上，進而較佳為3.0GPa以上。進而，在200℃之儲存彈性模數E’能夠設為0.5GPa以上，較佳為0.7GPa以上，進而較佳為0.8GPa以上。Furthermore, the storage elastic modulus E' at 30°C of the cured product obtained by curing the negative photosensitive resin composition of this embodiment at 170°C for 4 hours can be set to 2.0 GPa or more, preferably 2.5 GPa or more, and further Preferably it is 3.0 GPa or more. Furthermore, the storage elastic modulus E' at 200°C can be set to 0.5 GPa or more, preferably 0.7 GPa or more, and still more preferably 0.8 GPa or more.
關於本實施形態之負型感光性樹脂組成物的黏度，能夠依據所需的樹脂膜的厚度適當設定。關於負型感光性樹脂組成物的黏度的調節，能夠藉由添加溶劑來進行。The viscosity of the negative photosensitive resin composition of the present embodiment can be appropriately set according to the thickness of the required resin film. The adjustment of the viscosity of a negative photosensitive resin composition can be performed by adding a solvent.
由本實施形態的負型感光性樹脂組成物獲得之膜等硬化物的耐藥品性優異。 具體而言，在40℃，將膜在二甲基亞碸未達99質量%與氫氧化四甲基銨未達2質量%的溶液中浸漬10分鐘，其後用異丙醇充分清洗之後進行風乾，並測量處理後的膜厚。藉由下述公式計算處理後的膜厚與處理前的膜厚的膜厚變化率，並作為膜的減少率進行評價。 公式：膜的減少率（%）=｛（浸漬後的膜厚-浸漬前的膜厚）/浸漬前的膜厚×100（%）｝ Cured products such as films obtained from the negative photosensitive resin composition of this embodiment are excellent in chemical resistance. Specifically, at 40° C., the membrane was immersed in a solution of up to 99% by mass of dimethylsulfoxide and up to 2% by mass of tetramethylammonium hydroxide for 10 minutes, and then sufficiently washed with isopropanol. Air dry and measure the film thickness after treatment. The film thickness change rate between the film thickness after the treatment and the film thickness before the treatment was calculated by the following formula, and evaluated as the reduction rate of the film. Formula: film reduction rate (%)={(film thickness after immersion-film thickness before immersion)/film thickness before immersion×100(%)}
膜厚變化率為40%以下為較佳，30%以下為更佳。藉此，即使在將硬化膜供於浸漬於二甲基亞碸中之步驟中之情況，膜厚亦幾乎不會減少。因此，可以獲得即使在供於該步驟中之後亦能夠維持功能之硬化膜。The film thickness change rate is preferably 40% or less, more preferably 30% or less. Thereby, even when the cured film is subjected to the step of immersing in dimethyl sulfide, the film thickness hardly decreases. Therefore, it is possible to obtain a cured film capable of maintaining functions even after being subjected to this step.
本實施形態的負型感光性樹脂組成物的硬化收縮得到抑制，將其以使乾燥後的膜厚成為10μm的方式旋塗於矽晶圓表面，在120℃預烘烤3分鐘之後，用高壓水銀燈進行600mJ/cm 2的曝光，其後在氮氣環境下，在170℃進行120分鐘的熱處理，從而製備了膜，在此情況，將前述預烘烤後的膜的膜厚設為膜厚A且將前述熱處理後的膜的膜厚設為膜厚B時之由下述公式計算之硬化收縮率能夠較佳設為12%以下，更佳設為10%以下。 公式：硬化收縮率[%]=｛（膜厚A-膜厚B）/膜厚A｝×100 The curing shrinkage of the negative-type photosensitive resin composition of this embodiment is suppressed, and it is spin-coated on the surface of a silicon wafer so that the film thickness after drying becomes 10 μm. After pre-baking at 120° C. for 3 minutes, The mercury lamp was exposed to 600mJ/cm 2 , and then heat-treated at 170°C for 120 minutes in a nitrogen atmosphere to prepare a film. In this case, the film thickness of the film after the aforementioned prebaking was defined as film thickness A In addition, when the film thickness of the film after the heat treatment is taken as film thickness B, the cure shrinkage rate calculated by the following formula can be preferably 12% or less, more preferably 10% or less. Formula: hardening shrinkage [%]={(film thickness A-film thickness B)/film thickness A}×100
本實施形態的負型感光性樹脂組成物的耐熱性高，關於所獲得之膜，藉由熱重示差熱的同時測量（TG-DTA）而測得之重量減少溫度（Td5）能夠設為200℃以上，較佳為300℃以上。The negative photosensitive resin composition of this embodiment has high heat resistance, and the weight loss temperature (Td5) measured by thermogravimetric differential thermal simultaneous measurement (TG-DTA) can be set to 200 for the obtained film. °C or higher, preferably 300 °C or higher.
由本實施形態的負型感光性樹脂組成物構成之膜的硬化收縮得到抑制，線性熱膨脹係數（CTE）能夠設為200ppm/℃以下，較佳為100ppm/℃以下。The curing shrinkage of the film composed of the negative photosensitive resin composition of this embodiment is suppressed, and the coefficient of linear thermal expansion (CTE) can be set to 200 ppm/°C or less, preferably 100 ppm/°C or less.
由本實施形態的負型感光性樹脂組成物構成之膜的機械強度優異，在25℃的彈性模數能夠設為1.0～5.0GPa，較佳為1.5～3.0GPa。The film composed of the negative photosensitive resin composition of this embodiment is excellent in mechanical strength, and the modulus of elasticity at 25° C. can be 1.0 to 5.0 GPa, preferably 1.5 to 3.0 GPa.
（用途） 本實施形態的負型感光性樹脂組成物用於形成永久膜、阻劑（resist）層等半導體裝置用樹脂膜。該等之中，就均衡地表現出預烘烤後的負型感光性樹脂組成物及Al襯墊（pad）的密接性提高與顯影時的負型感光性樹脂組成物的殘渣的產生的抑制之觀點、提高熱處理後的負型感光性樹脂組成物的硬化膜與金屬的密接性之觀點以及提高熱處理後的負型感光性樹脂組成物的耐藥品性之觀點而言，用於使用永久膜之用途中為較佳。 (use) The negative photosensitive resin composition of this embodiment is used to form resin films for semiconductor devices such as permanent films and resist layers. Among them, the improvement of the adhesiveness of the negative photosensitive resin composition after prebaking and the Al pad and the suppression of the residue generation of the negative photosensitive resin composition during development are exhibited in a balanced manner. From the point of view, from the point of view of improving the adhesion between the cured film of the negative photosensitive resin composition after heat treatment and the metal, and from the point of view of improving the chemical resistance of the negative photosensitive resin composition after heat treatment, it is used for permanent film It is better in the application.
再者，在本實施形態中，樹脂膜包括負型感光性樹脂組成物的硬化膜。亦即，本實施形態之樹脂膜為使負型感光性樹脂組成物硬化而成者。In addition, in the present embodiment, the resin film includes a cured film of a negative photosensitive resin composition. That is, the resin film of this embodiment is what hardened the negative photosensitive resin composition.
上述永久膜由樹脂膜構成，該樹脂膜藉由下述方式而獲得：對負型感光性樹脂組成物進行預烘烤、曝光及顯影，並將其圖案形成為所需的形狀之後，藉由進行熱處理使其硬化。永久膜能夠用作半導體裝置的保護膜、層間膜、壩材等。The above-mentioned permanent film is composed of a resin film, which is obtained by prebaking, exposing and developing the negative photosensitive resin composition, and patterning it into a desired shape. Heat treatment to harden it. The permanent film can be used as a protective film, interlayer film, dam material, etc. of a semiconductor device.
上述阻劑層由樹脂膜構成，該樹脂膜藉由下述方式而獲得：例如藉由旋塗、輥塗、淋塗、浸塗、噴塗、刮塗等方法將負型感光性樹脂組成物塗布於被阻劑層遮蔽之對象上，並從負型感光性樹脂組成物中去除溶劑。The above-mentioned resist layer is composed of a resin film obtained by, for example, coating a negative-type photosensitive resin composition by spin coating, roll coating, flow coating, dip coating, spray coating, blade coating, and the like. On the object masked by the resist layer, and remove the solvent from the negative photosensitive resin composition.
將本實施形態之半導體裝置的一例示於圖1中。
本實施形態之半導體裝置100能夠設為具備上述樹脂膜之半導體裝置。具體而言，能夠將半導體裝置100中由鈍化膜32、絕緣層42及絕緣層44構成的群中的1個以上設為包含本實施形態的硬化物之樹脂膜。其中，樹脂膜為上述永久膜為較佳。
An example of the semiconductor device of this embodiment is shown in FIG. 1 .
The
半導體裝置100例如為半導體晶片。此時，例如可以藉由將半導體裝置100經由凸塊52搭載於配線基板上而獲得半導體封裝。The
半導體裝置100具備設置有電晶體等半導體元件之半導體基板和設置於半導體基板上之多層配線層（未圖示。）。在多層配線層中的最上層設置有層間絕緣膜30和設置於層間絕緣膜30上之最上層配線34。最上層配線34例如由鋁Al構成。又，在層間絕緣膜30上及最上層配線34上設置有鈍化膜32。在鈍化膜32的一部分中設置有暴露最上層配線34之開口。The
在鈍化膜32上設置有再配線層40。再配線層40具有設置於鈍化膜32上之絕緣層42、設置於絕緣層42上之再配線46以及設置於絕緣層42上及再配線46上之絕緣層44。在絕緣層42形成有與最上層配線34連接之開口。再配線46形成於絕緣層42上及設置於絕緣層42之開口內，並與最上層配線34連接。在絕緣層44設置有與再配線46連接之開口。A
在設置於絕緣層44之開口內例如經由UBM（Under Bump Metallurgy：凸塊下金屬）層50形成有凸塊52。半導體裝置100例如經由凸塊52與配線基板等連接。
以上，對本發明的實施形態進行了敘述，然而，該等為本發明的例示，能夠在不損害本發明的效果的範圍採用除了上述以外的各種結構。
[實施例]
The
以下，藉由實施例對本發明進行更詳細地說明，然而，本發明並不限定於該等。 在聚合物的合成中使用了以下化合物。 Hereinafter, the present invention will be described in more detail by way of examples, however, the present invention is not limited thereto. The following compounds were used in the synthesis of the polymer.
下述式所表示之4,4-二胺基-3,3-二乙基-5,5-二甲基二苯基甲烷（以下，亦表示為MED-J）
下述式所表示之2,2-雙（3-胺基-4-羥基苯基）丙烷（以下，亦表示為BAPA）
下述式所表示之2,2-雙（3-胺基-4-羥基苯基）六氟丙烷（以下，亦表示為BAFA）
下述式所表示之4,4’-二胺基-2,2’-雙（三氟甲基）聯苯（以下，亦表示為TFMB）
下述式所表示之4,4’-（六氟亞異丙基）雙[（4-胺基苯氧基）苯]（以下，亦表示為HFBAPP）
下述式所表示之4-[4-（1,3-二氧代異苯并呋喃-5-基羰氧基）-2,3,5-三甲基苯基]-2,3,6-三甲基苯基-1,3-二氧代異苯并呋喃-5-羧酸酯（以下，亦表示為TMPBP-TME）
下述式所表示之對伸苯基雙（偏苯三酸酐）（以下，亦表示為TMHQ）
[實施例1]
首先，在具備攪拌機及冷卻管之適當尺寸的反應容器中加入了MED-J 29.01g（102.7mmol）、BAPA 26.53g（102.7mmol）及TMPBP-TME 151.29g（244.6mmol）。其後，在反應容器中進一步添加了GBL 620.49g。
將氮氣通氣10分鐘之後，一邊攪拌一邊將溫度升溫至60℃，並反應了1.5小時。其後，進一步在180℃反應3小時以使雙胺基苯酚與酸酐進行聚合，從而製作了聚合溶液。
對聚合物進行了GPC測量，其結果，重量平均分子量Mw為20,000，多分散性（重量平均分子量Mw/數量平均分子量Mn）為1.98。
接著，在所獲得之聚醯亞胺溶液總量（羥基換算205.4mmol）中加入了丙烯酸2-異氰酸基乙酯（以下，亦表示為AOI、SHOWA DENKO CO.,LTD.製）57.99g（410.9mmol）和γ-丁內酯（GBL）177.84g。其後，一邊攪拌一邊將溫度升溫至120℃，並反應了6小時。
用四氫呋喃稀釋所獲得之反應溶液來製作稀釋液，接著將稀釋液滴加到甲醇中，從而使白色固體析出。回收所獲得之白色固體，在溫度40℃進行真空乾燥，從而獲得了聚合物212.35g。
對聚合物進行了GPC測量，其結果，重量平均分子量Mw為26,100，多分散性（重量平均分子量Mw/數量平均分子量Mn）為2.30。
又，進行了
1H-NMR測量，其結果，在芳香族區域（6.8ppm～8.8ppm）中以與質子數對應之面積比確認了峰值。
又，依據芳香族區域（6.8ppm～8.8ppm）與烯烴區域（5.8ppm～6.3ppm）的面積比，交聯基的導入率為83%。
導入有交聯基之聚合物在其一部分中包含下述式所表示之重複單元。
[實施例2] 首先，在具備攪拌機及冷卻管之適當尺寸的反應容器中加入了MED-J 9.67g（34.2mmol）、BAPA 2.95g（11.4mmol）及TMPBP-TME 33.62g（54.3mmol）。其後，在反應容器中進一步添加了GBL138.71g。 將氮氣通氣10分鐘之後，一邊攪拌一邊將溫度升溫至60℃，並反應了1.5小時。其後，進一步在180℃反應3小時以使雙胺基苯酚與酸酐進行聚合，從而製作了聚合溶液。 對聚合物進行了GPC測量，其結果，重量平均分子量Mw為21,500，多分散性（重量平均分子量Mw/數量平均分子量Mn）為2.02。 接著，在所獲得之聚醯亞胺溶液總量（羥基換算22.8mmol）中加入了丙烯酸2-異氰酸基乙酯（以下，亦表示為AOI、SHOWA DENKO CO.,LTD.製）6.44g（45.6mmol）和γ-丁內酯（GBL）43.02g。其後，一邊攪拌一邊將溫度升溫至120℃，並反應了6小時。 用四氫呋喃稀釋所獲得之反應溶液來製作稀釋液，接著將稀釋液滴加到甲醇中，從而使白色固體析出。回收所獲得之白色固體，在溫度40℃進行真空乾燥，從而獲得了聚合物43.73g。 對聚合物進行了GPC測量，其結果，重量平均分子量Mw為22,800，多分散性（重量平均分子量Mw/數量平均分子量Mn）為2.15。 又，進行了 1H-NMR測量，其結果，在芳香族區域（6.8ppm～8.8ppm）中以與質子數對應之面積比確認了峰值。 又，依據芳香族區域（6.8ppm～8.8ppm）與烯烴區域（5.8ppm～6.3ppm）的面積比，交聯基的導入率為100%。 導入有交聯基之聚合物在其一部分中包含前述式所表示之重複單元。 [Example 2] First, 9.67 g (34.2 mmol) of MED-J, 2.95 g (11.4 mmol) of BAPA, and 33.62 g (54.3 mmol) of TMPBP-TME were placed in a reaction vessel of an appropriate size equipped with a stirrer and a cooling pipe. Thereafter, GBL138.71 g was further added to the reaction container. After blowing nitrogen gas for 10 minutes, the temperature was raised to 60° C. while stirring, and the reaction was carried out for 1.5 hours. Thereafter, the reaction was further carried out at 180° C. for 3 hours to polymerize bisaminophenol and acid anhydride to prepare a polymerization solution. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 21,500, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.02. Next, 6.44 g of 2-isocyanatoethyl acrylate (hereinafter also referred to as AOI, manufactured by SHOWA DENKO CO., LTD.) was added to the total amount of the obtained polyimide solution (22.8 mmol in terms of hydroxyl group) (45.6mmol) and γ-butyrolactone (GBL) 43.02g. Thereafter, the temperature was raised to 120° C. while stirring, and the mixture was reacted for 6 hours. The obtained reaction solution was diluted with tetrahydrofuran to prepare a diluted solution, and the diluted solution was added dropwise to methanol to precipitate a white solid. The obtained white solid was recovered and vacuum-dried at a temperature of 40° C. to obtain 43.73 g of a polymer. As a result of GPC measurement of the polymer, the weight average molecular weight Mw was 22,800, and the polydispersity (weight average molecular weight Mw/number average molecular weight Mn) was 2.15. Furthermore, as a result of 1 H-NMR measurement, peaks were confirmed in the aromatic region (6.8 ppm to 8.8 ppm) at an area ratio corresponding to the number of protons. Also, the introduction rate of the crosslinking group was 100% based on the area ratio of the aromatic region (6.8 ppm to 8.8 ppm) to the olefin region (5.8 ppm to 6.3 ppm). The polymer into which the crosslinking group is introduced contains the repeating unit represented by the said formula in a part.
[實施例3]
首先，在具備攪拌機及冷卻管之適當尺寸的反應容器中加入了MED-J 12.89g（45.7mmol）和TMPBP-TME 33.62g（54.3mmol）。其後，在反應容器中進一步添加了GBL 125.58g。
將氮氣通氣10分鐘之後，一邊攪拌一邊將溫度升溫至60℃，並反應了1.5小時。其後，進一步在180℃反應3小時以使雙胺基苯酚與酸酐進行聚合，從而製作了聚合溶液。
對聚合物進行了GPC測量，其結果，重量平均分子量Mw為23,600，多分散性（重量平均分子量Mw/數量平均分子量Mn）為2.05。
接著，在所獲得之聚醯亞胺溶液總量（無末端酸換算17.4mmol）中加入了丙烯酸2-異氰酸基乙酯（以下，亦表示為AOI、SHOWA DENKO CO.,LTD.製）4.91g（34.8mmol）和γ-丁內酯（GBL）44.06g。其後，一邊攪拌一邊將溫度升溫至120℃，並反應了6小時。
用四氫呋喃稀釋所獲得之反應溶液來製作稀釋液，接著將稀釋液滴加到甲醇中，從而使白色固體析出。回收所獲得之白色固體，在溫度40℃進行真空乾燥，從而獲得了聚合物41.73g。
對聚合物進行了GPC測量，其結果，重量平均分子量Mw為23,100，多分散性（重量平均分子量Mw/數量平均分子量Mn）為2.09。
又，進行了
1H-NMR測量，其結果，在芳香族區域（6.9ppm～8.9ppm）中以與質子數對應之面積比確認了峰值。
又，藉由依據芳香族區域（6.9ppm～8.9ppm）與烯烴區域（5.8ppm～6.5ppm）的面積比和聚合度的計算，對末端的交聯基的導入率為100%。
所獲得之聚合物在其一部分中包含下述式所表示之重複單元，在末端導入有交聯基。
[實施例4～7、比較例1～4] 關於實施例4～7、比較例1～4，除了表1中所記載的條件以外，藉由與實施例1相同的方法進行了合成。 關於比較例1、2，在聚合反應中凝膠化而難以繼續反應，因此將在GBL中的溶劑溶解性設為×。 [Examples 4-7, Comparative Examples 1-4] About Examples 4-7 and Comparative Examples 1-4, except the conditions described in Table 1, it synthesize|combined by the method similar to Example 1. In Comparative Examples 1 and 2, the reaction was difficult to continue due to gelation during the polymerization reaction, so the solvent solubility in GBL was made x.
[在有機溶劑中之溶解性] 依據以下基準評價了在實施例1～6、比較例3、4中所獲得之負型感光性聚合物在γ-丁內酯（GBL）中之溶解性。將結果示於表2中。 （溶解性的評價基準） ○：聚合物溶解5質量%以上 △：聚合物溶解1～5質量% ×：聚合物溶解未達1質量% [Solubility in organic solvents] The solubility of the negative photosensitive polymer obtained in Examples 1 to 6 and Comparative Examples 3 and 4 in γ-butyrolactone (GBL) was evaluated on the basis of the following criteria. The results are shown in Table 2. (Evaluation criteria for solubility) ○: 5% by mass or more of the polymer dissolved △: 1 to 5% by mass of polymer dissolved ×: Dissolution of the polymer does not reach 1% by mass
[耐水解性] 在以下條件測量了在實施例及比較例中所獲得之負型感光性聚合物的重量平均分子量的減少率。 （條件（未添加三乙胺）） 在負型感光性聚合物100質量份中添加γ-丁內酯400質量份、4-甲基四氫吡喃200質量份及水50質量份並在100℃攪拌了6小時之情況，藉由下述公式進行計算。將結果示於表2中。 公式：[（試驗前的重量平均分子量-試驗後的重量平均分子量）/試驗前的重量平均分子量]×100 （條件（添加三乙胺）） 在負型感光性聚合物100質量份中添加三乙胺10質量份、γ-丁內酯400質量份、4-甲基四氫吡喃200質量份及水50質量份並在100℃攪拌了6小時之情況，藉由下述公式進行計算。將結果示於表2中。 公式：[（試驗前的重量平均分子量-試驗後的重量平均分子量）/試驗前的重量平均分子量]×100 [hydrolysis resistance] The reduction rate of the weight average molecular weight of the negative photosensitive polymer obtained in the Example and the comparative example was measured under the following conditions. (Condition (without addition of triethylamine)) When 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of a negative photosensitive polymer and stirred at 100° C. for 6 hours, the The following formula is used for calculation. The results are shown in Table 2. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100 (conditions (addition of triethylamine)) 10 parts by mass of triethylamine, 400 parts by mass of γ-butyrolactone, 200 parts by mass of 4-methyltetrahydropyran, and 50 parts by mass of water were added to 100 parts by mass of a negative photosensitive polymer, and stirred at 100°C. In the case of 6 hours, it is calculated by the following formula. The results are shown in Table 2. Formula: [(weight average molecular weight before test-weight average molecular weight after test)/weight average molecular weight before test]×100
[伸長率] 將包含在實施例、比較例中所獲得之聚合物溶液（聚合物100質量份）、5質量份的熱自由基產生劑Perkadox BC、2質量份的密接助劑KBM-503P及0.1質量份的界面活性劑FC4432之組成物旋塗於矽晶圓表面，在110℃預烘烤3分鐘之後，在氮氣下，在170℃進行240分鐘的熱處理，從而製備了膜。再者，對各成分的詳細情況已記載於後述。 在23℃的環境下，對從所獲得之膜切出之試驗片（6.5mm×60mm×10μm厚）實施了拉伸試驗（拉伸速度：5mm/分鐘）。關於拉伸試驗，使用ORIENTEC CO., LTD.製拉伸試驗機（Tensilon RTC-1210A）來進行。測量10片試驗片，依據斷裂之距離和初始距離計算出拉伸伸長率，並求出伸長率的最大值。將結果示於表2中。 [Elongation] The polymer solution (100 parts by mass of polymer) obtained in Examples and Comparative Examples, 5 parts by mass of thermal radical generator Perkadox BC, 2 parts by mass of adhesion aid KBM-503P and 0.1 parts by mass of The composition of the surfactant FC4432 was spin-coated on the surface of the silicon wafer, pre-baked at 110°C for 3 minutes, and then heat-treated at 170°C for 240 minutes under nitrogen to prepare a film. In addition, the detail about each component is described later. A tensile test was performed on a test piece (6.5 mm×60 mm×10 μm thick) cut out from the obtained film in an environment of 23° C. (tensile speed: 5 mm/min). The tensile test was performed using a tensile testing machine (Tensilon RTC-1210A) manufactured by ORIENTEC CO., LTD. Measure 10 test pieces, calculate the tensile elongation according to the breaking distance and the initial distance, and obtain the maximum value of the elongation. The results are shown in Table 2.
[表2]
如表2所示，推測由於在實施例中所獲得之本發明的負型感光性聚合物的對有機溶劑的溶解性及伸長率優異，並且水解得到抑制，因此伸長率的降低少且機械強度的降低得到抑制。As shown in Table 2, it is presumed that the negative photosensitive polymer of the present invention obtained in Examples has excellent solubility in organic solvents and elongation, and hydrolysis is suppressed, so the reduction in elongation is small and the mechanical strength is low. decrease is suppressed.
在製備負型感光性樹脂組成物時，使用了以下化合物。 （交聯劑） ·丙烯酸酯化合物1：二新戊四醇六丙烯酸酯（SHIN-NAKAMURA CHEMICAL CO, LTD.製，NK酯A-DPH） When preparing the negative photosensitive resin composition, the following compounds were used. (crosslinking agent) ・Acrylic ester compound 1: dipenteoerythritol hexaacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO, LTD., NK ester A-DPH)
（聚合起始劑）
·光自由基產生劑：2-（二甲基胺基）-1-（4-（4-
（密接助劑） ·密接助劑1：3-甲基丙烯醯氧基丙基三甲氧基矽烷（KBM-503P，Shin-Etsu Chemical Co., Ltd.製） (adhesion aid) Adhesion aid 1: 3-methacryloxypropyltrimethoxysilane (KBM-503P, manufactured by Shin-Etsu Chemical Co., Ltd.)
（界面活性劑） ·界面活性劑1：具有氟碳鏈之界面活性劑（FC-4432，Sumitomo 3M Limited製） (surfactant) · Surfactant 1: Surfactant having a fluorocarbon chain (FC-4432, manufactured by Sumitomo 3M Limited)
（溶劑） ·溶劑1：γ-丁內酯（GBL） (solvent) Solvent 1: γ-butyrolactone (GBL)
[實施例8] （負型感光性樹脂組成物的製備） 混合實施例5的聚合物（聚合物100質量份）和將表3所示之成分以成為22wt%GBL溶液的方式預先溶解而獲得者，從而製備了感光性樹脂組成物。 將所獲得之負型感光性樹脂組成物以使乾燥後的膜厚成為10μm的方式旋塗於矽晶圓表面，在120℃預烘烤3分鐘之後，用高壓水銀燈進行600mJ/cm 2的曝光，其後，在氮氣環境下，在170℃進行120分鐘的熱處理，從而製備了膜。 關於所獲得之膜，藉由下述方法測量玻璃轉移溫度（Tg）及伸長率，並對圖案形成特性進行了評價。將結果示於表3中。 [Example 8] (Preparation of Negative Photosensitive Resin Composition) The polymer of Example 5 (100 parts by mass of the polymer) was mixed and the components shown in Table 3 were previously dissolved so as to become a 22 wt % GBL solution. Or, thereby preparing a photosensitive resin composition. The obtained negative photosensitive resin composition was spin-coated on the surface of the silicon wafer so that the film thickness after drying was 10 μm, pre-baked at 120°C for 3 minutes, and then exposed to 600mJ/cm 2 with a high-pressure mercury lamp , and thereafter, heat treatment was performed at 170° C. for 120 minutes in a nitrogen atmosphere, thereby preparing a film. About the obtained film, the glass transition temperature (Tg) and elongation were measured by the following method, and the pattern formation characteristic was evaluated. The results are shown in Table 3.
[玻璃轉移溫度（Tg）] 從在實施例8中所獲得之膜切出8mm×40mm的試驗片，使用動態黏彈性測量裝置（DMA裝置，TA Instruments.製，Q800），以升溫速度5℃/min、頻率1Hz對該試驗片進行動態黏彈性測量，並將損耗正切tanδ顯示最大值之溫度作為玻璃轉移溫度進行了測量。 [Glass transition temperature (Tg)] A test piece of 8 mm x 40 mm was cut out from the film obtained in Example 8, and the test was performed at a heating rate of 5° C./min and a frequency of 1 Hz using a dynamic viscoelasticity measuring device (DMA device, manufactured by TA Instruments., Q800). The dynamic viscoelasticity measurement was performed on the sheet, and the temperature at which the loss tangent tanδ showed the maximum value was measured as the glass transition temperature.
[伸長率] 在23℃的環境中，對從在實施例8中所獲得之膜切出之試驗片（6.5mm×60mm×10μm厚）實施了拉伸試驗（拉伸速度：5mm/分鐘）。拉伸試驗係使用ORIENTEC CO., LTD.製拉伸試驗機（Tensilon RTC-1210A）來進行。測量5片試驗片，並將斷裂點的應力平均化者設為強度。依據斷裂之距離和初始距離計算出拉伸伸長率，並求出伸長率的平均值和最大值。 進而，在溫度130℃、相對濕度85%RH的條件，對從在實施例8中所獲得之膜切出之前述試驗片進行96小時的HAST（不飽和加壓蒸氣試驗）之後，以與前述相同的方式求出伸長率的平均值和最大值。 [Elongation] A tensile test was performed on a test piece (6.5 mm×60 mm×10 μm thick) cut out from the film obtained in Example 8 in an environment of 23° C. (tensile speed: 5 mm/min). The tensile test was performed using a tensile testing machine (Tensilon RTC-1210A) manufactured by ORIENTEC CO., LTD. Five test pieces were measured, and the stress averaged at the breaking point was defined as the strength. The tensile elongation was calculated according to the distance to break and the initial distance, and the average value and maximum value of the elongation were obtained. Furthermore, under the conditions of a temperature of 130° C. and a relative humidity of 85% RH, the aforementioned test piece cut out from the film obtained in Example 8 was subjected to HAST (unsaturated pressurized steam test) for 96 hours, and compared with the aforementioned The average value and maximum value of the elongation are obtained in the same manner.
[與圖案形成特性相關之評價] 如下確認了實施例8的感光性樹脂組成物藉由曝光和顯影能夠充分地進行圖案形成的情況。 使用旋轉塗布機將實施例8的感光性樹脂組成物塗布於8英寸的矽晶圓上。塗布之後，在大氣下，藉由加熱板在110℃預烘烤3分鐘，從而獲得了膜厚約5.0μm的塗膜。 穿過繪製有寬度20μm的通孔圖案之遮罩，向該塗膜照射了i射線。關於照射，使用了i射線步進機（Nikon Corporation製，NSR-4425i）。 曝光之後，使用環戊酮作為顯影液噴霧顯影40秒，進一步使用PGMEA作為顯影液噴霧顯影10秒，以溶解去除未曝光部，從而獲得了通孔圖案。 使用桌上型SEM觀察了所獲得之通孔圖案的截面。將通孔圖案的底面與開口部的中間的高度中之寬度設為通孔寬度，並依據以下基準進行了評價。 圖案形成性良好：開口有20μm的通孔圖案 圖案形成性不良：未開口有20μm的通孔圖案 由實施例8的感光性樹脂組成物獲得之塗膜的圖案形成性良好。 [Evaluation related to pattern formation characteristics] It was confirmed that the photosensitive resin composition of Example 8 can sufficiently perform pattern formation by exposure and image development as follows. The photosensitive resin composition of Example 8 was coated on an 8-inch silicon wafer using a spin coater. After the coating, the coating was prebaked at 110° C. for 3 minutes on a hot plate in the atmosphere, thereby obtaining a coating film with a film thickness of about 5.0 μm. The coating film was irradiated with i-rays through a mask in which a via-hole pattern with a width of 20 μm was drawn. For irradiation, an i-ray stepper (manufactured by Nikon Corporation, NSR-4425i) was used. After the exposure, cyclopentanone was used as a developer for 40 seconds, and PGMEA was used for 10 seconds to dissolve and remove the unexposed portion, thereby obtaining a via hole pattern. The cross-section of the obtained via hole pattern was observed using a desktop SEM. The width in the height between the bottom surface of the via pattern and the middle of the opening was defined as the via width, and evaluated based on the following references. Good pattern formation: via pattern with 20μm opening Poor pattern formation: 20 μm via hole pattern without opening The pattern formability of the coating film obtained from the photosensitive resin composition of Example 8 was favorable.
[表3]
如表3中所記載，明確了由包含本發明的負型感光性聚合物之負型感光性樹脂組成物獲得之膜的伸長率優異，進而由於包含耐水解性優異之負型感光性聚合物，因此即使在HAST試驗之後，機械強度亦優異。又，確認到圖案形成性亦良好，適合用作負型感光性樹脂組成物。As described in Table 3, it is clear that the elongation of the film obtained from the negative photosensitive resin composition containing the negative photosensitive polymer of the present invention is excellent, and because the negative photosensitive polymer excellent in hydrolysis resistance is contained , so even after the HAST test, the mechanical strength is excellent. Moreover, it confirmed that pattern formability is also favorable and it is suitable as a negative photosensitive resin composition.
本申請主張基於2021年6月25日申請之日本申請特願2021-105682號之優先權，並將該揭示的所有內容編入本文中。This application claims priority based on Japanese Patent Application No. 2021-105682 filed on June 25, 2021, and incorporates all the contents of the disclosure into this document.
100:半導體裝置 30:層間絕緣膜 32:鈍化膜 34:最上層配線 40:再配線層 42:絕緣層 44:絕緣層 46:再配線 50:UBM層 52:凸塊 100: Semiconductor device 30: interlayer insulating film 32: Passivation film 34: Top layer wiring 40: Redistribution layer 42: Insulation layer 44: Insulation layer 46: Rewiring 50: UBM layer 52: Bump
[圖1]係本實施形態的半導體裝置的概略剖面圖。[ Fig. 1] Fig. 1 is a schematic cross-sectional view of a semiconductor device according to the present embodiment.
30:層間絕緣膜 30: interlayer insulating film
32:鈍化膜 32: Passivation film
34:最上層配線 34: Top layer wiring
40:再配線層 40: Redistribution layer
42:絕緣層 42: Insulation layer
44:絕緣層 44: Insulation layer
46:再配線 46: Rewiring
50:UBM層 50: UBM layer
52:凸塊 52: Bump
100:半導體裝置 100: Semiconductor device
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