TW202244131A - Photosensitive resin composition - Google Patents

Abstract

This photosensitive resin composition comprises: a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings; and a solvent.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition, a resin film obtained from the composition, a photoresist film using the composition, a method for manufacturing a substrate with a cured relief pattern, a substrate with a cured relief pattern, and a substrate having a cured relief pattern. Hardened semiconductor devices with relief patterns.

In the past, polyimide resins with excellent heat resistance, electrical properties, and mechanical properties have been used for insulating materials of electronic parts, passivation films, surface protection films, and interlayer insulating films of semiconductor devices. Among the polyimide resins, those provided in the form of photosensitive polyimide precursors can be easily processed by thermal imidization through the coating, exposure, development, and aging of the precursors. Form a heat-resistant relief pattern film. Compared with the conventional non-photosensitive polyimide resin, such photosensitive polyimide precursor has the feature that the number of steps may be greatly reduced.

Patent Document 1 and Patent Document 2 propose a photosensitive resin composition including polyamic acid or polyimide having a (meth)acryloxy group. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-347404 [Patent Document 2] Japanese National Publication No. 2012-516927

(Problem to be solved by the invention)

In recent years, semiconductor devices need to transmit and process large-capacity information at high speed, and the high frequency of electrical signals has been progressing. Because high-frequency electrical signals are easily attenuated, transmission loss needs to be reduced. Therefore, a low dielectric tangent is required for resins used in semiconductor devices. On the other hand, resins with low dielectric tangent tend to be brittle. For example, during heat treatment steps such as solder reflow steps, sometimes they cannot follow the thermal expansion of adjacent materials, resulting in cracks and reduced interlayer adhesion. affair. Therefore, resins used in semiconductor devices need to have high tensile elongation.

In addition, when forming a hardened relief pattern, development with a developer is performed, and generally an alkaline aqueous developer or an organic solvent developer is used. In order to obtain the photosensitive resin with hardened relief pattern, it is divided into positive type in which the photosensitive resin in the exposed part dissolves in the developer solution due to exposure and development, and the photosensitive resin in the unexposed part remains, and the photosensitive resin in the unexposed part dissolves in the developing solution. Negative type with liquid and photosensitive resin remaining in the exposed part. In particular, the negative type has poorer resolution than the positive type, but it is easy to thicken and thinn the film and has excellent reliability. It is used in the manufacture of semiconductor devices that require such characteristics. However, the conventional negative photosensitive resin containing polyamide acid has a very high solubility in alkaline aqueous developer, so it is difficult to control the dissolution rate, and it may be difficult to obtain the desired relief pattern. Furthermore, the negative photosensitive resin containing polyamic acid has high affinity with alkaline aqueous developer, so it is easy to swell during development, and there are problems such as easy peeling of the formed undulating pattern from the substrate due to the stress generated during drying. Therefore, the negative-type photosensitive resin containing polyamide acid is suitable for organic solvent development where the control of the dissolution rate is relatively easy and the concern of substrate peeling is less.

Therefore, it is necessary to seek a photosensitive resin composition that can be developed by an organic solvent, and the obtained cured film has a low dielectric tangent and a high tensile elongation. However, the photosensitive resin compositions of Patent Document 1 and Patent Document 2 do not fully meet these characteristics.

In view of the foregoing, the object of the present invention is to provide a photosensitive resin composition that can be developed with an organic solvent, and the obtained cured film has a low dielectric tangent and high tensile elongation, a resin film obtained from the composition, and a A photoresist thin film containing the composition, a manufacturing method of a substrate with a hardened relief pattern, a substrate with a hardened relief pattern, and a semiconductor device with a hardened relief pattern. (How to solve the problem)

The inventors of the present case worked hard to achieve the above-mentioned problems, and found that: by making the photosensitive resin composition contain an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings The reaction product can be developed by an organic solvent, and the obtained cured film has a low dielectric tangent and a photosensitive resin composition with high tensile elongation, which is the completion of the present invention.

式(1)中，Ar ₁表示具有光聚合性基及芳香族環之2價有機基，Ar ₂表示具有3個以上之芳香族環之4價有機基， [化2]

式(2)中，Ar ₃表示具有光聚合性基及芳香族環之2價有機基，Ar ₄表示具有3個以上之芳香族環之4價有機基。 [4] 如[3]之感光性樹脂組成物，其中，該式(1)中之Ar ₂及該式(2)中之Ar ₄係下式(3)表示之4價有機基， [化3]

式(3)中，X ₁及X ₂各自獨立地表示直接鍵結、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵或磺醯基鍵;R ₁及R ₂各自獨立地表示亦可經取代之碳原子數1至6之烷基;Y表示下式(3-1)或(3-2)表示之2價有機基;n1及n2各自獨立地表示0至3之整數;R ₁有多個時，多個R ₁可相同也可不同;R ₂有多個時，多個R ₂可相同也可不同;＊表示原子鍵; [化4]

式(3-1)中，Z ₁表示直接鍵結、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、或磺醯基鍵;R ₃及R ₄各自獨立地表示亦可經取代之碳原子數1至6之烴基;m1表示0至3之整數;n3及n4各自獨立地表示0至4之整數;Z ₁有多個時，多個Z ₁可相同也可不同;n4有多個時，多個n4可相同也可不同;R ₃有多個時，多個R ₃可相同也可不同;R ₄有多個時，多個R ₄可相同也可不同;＊表示原子鍵; 式(3-2)中，Z ₂表示下式(4)或(5)表示之2價有機基;R ₅及R ₆各自獨立地表示亦可經取代之碳原子數1至6之烴基;n5及n6各自獨立地表示0至4之整數;R ₅有多個時，多個R ₅可相同也可不同;R ₆有多個時，多個R ₆可相同也可不同;＊表示原子鍵; [化5]

式(4)中，R ₇及R ₈各自獨立地表示氫原子、或也可被鹵素原子取代之碳原子數1至6之烴基;＊表示原子鍵; 式(5)中，R ₉及R ₁₀各自獨立地表示亦可經取代之碳原子數1至6之伸烷基或亦可經取代之碳原子數6至10之伸芳基;＊表示原子鍵。 [5] 如[3]或[4]之感光性樹脂組成物，其中，該式(1)中之Ar ₁及該式(2)中之Ar ₃係下式(6)表示之2價有機基， [化6]

式(6)中，Z ₃表示醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵或脲鍵，Z ₄表示直接鍵結、酯鍵或醯胺鍵;Z ₅表示直接鍵結、醚鍵、酯鍵、醯胺鍵、胺甲酸酯鍵、脲鍵、硫醚鍵、或磺醯基鍵;m2表示0至1之整數;R ₁₁表示直接鍵結、或亦可被羥基取代之碳原子數2至6之伸烷基，R ₁₂表示氫原子或甲基;＊表示原子鍵。 [6] 如[5]之感光性樹脂組成物，其中，該式(6)中之Z ₃及Z ₄為酯鍵。 [7] 如[5]或[6]之感光性樹脂組成物，其中，該式(6)中之R ₁₁為1,2-伸乙基。 [8] 如[1]~[7]中任一項之感光性樹脂組成物，更含有光自由基聚合起始劑。 [9] 如[1]~[8]中任一項之感光性樹脂組成物，更含有交聯性化合物。 [10] 如[1]~[9]中任一項之感光性樹脂組成物，係絕緣膜形成用。 [11] 如[1]~[10]中任一項之感光性樹脂組成物，係負型感光性樹脂組成物。 [12] 一種樹脂膜，係如[1]~[11]中任一項之感光性樹脂組成物之塗佈膜之煅燒物。 [13] 如[12]之樹脂膜，係絕緣膜。 [14] 一種感光性阻劑薄膜，具有:基材薄膜;由如[1]~[11]中任一項之感光性樹脂組成物形成之感光性樹脂層;及表覆薄膜。 [15] 一種附硬化起伏圖案之基板之製造方法，包括下列步驟: (1)將如[1]~[11]中任一項之感光性樹脂組成物塗佈在基板上而將感光性樹脂層形成於該基板上; (2)將該感光性樹脂層進行曝光; (3)將該曝光後之感光性樹脂層進行顯影而形成起伏圖案; (4)將該起伏圖案進行加熱處理而形成硬化起伏圖案。 [16] 如[15]之附硬化起伏圖案之基板之製造方法，其中，該顯影中使用的顯影液為有機溶劑。 [17] 一種附硬化起伏圖案之基板，係利用如[15]或[16]之附硬化起伏圖案之基板之製造方法製造。 [18] 一種半導體裝置，具備半導體元件以及設於該半導體元件之上部或下部之硬化膜， 該硬化膜係由如[1]~[11]中任一項之感光性樹脂組成物形成之硬化起伏圖案。 (發明之效果) [1] A photosensitive resin composition comprising: a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent. [2] The photosensitive resin composition according to [1], wherein the reaction product is polyamic acid or polyimide obtained by dehydrating and ring-closing polyamic acid. [3] The photosensitive resin composition according to [2], wherein the polyamide acid has at least a structural unit represented by the following formula (1), and the polyimide has at least a structural unit represented by the following formula (2) , [Chem.1]

In the formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, Ar ₂ represents a 4-valent organic group having 3 or more aromatic rings, [Chem. 2]

In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having three or more aromatic rings. [4] The photosensitive resin composition as in [3], wherein Ar in the formula (1) and Ar in the formula ( ₂ ) are _tetravalent organic groups represented by the following formula (3), [Chem 3]

In formula (3), X ₁ and X ₂ each independently represent a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond or a sulfonyl bond; R ₁ and R ₂ each independently represent an alkyl group with 1 to 6 carbon atoms that may also be substituted; Y represents a divalent organic group represented by the following formula (3-1) or (3-2); n1 and n2 represent independently An integer from 0 to 3; when there are multiple R _1s , the multiple R _1s can be the same or different; when there are multiple R _2s , the multiple R _2s can be the same or different; * represents an atomic bond; [化4]

In formula (3-1), Z ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond, or a sulfonyl bond; R ₃ and R ₄ are each Independently represent a hydrocarbon group with a carbon number of 1 to 6 that may also be substituted; m1 represents an integer of 0 to 3; n3 and n4 each independently represent an integer of 0 to 4; when there are multiple Z ₁ , multiple Z ₁ can be _The same or different; when there are multiple _n4s , multiple _n4s can be the same or different; when there are multiple R3s, multiple R3s can be the same or different; when there are multiple R4s, multiple _R4s can be the same It can also be different; * represents an atomic bond; in formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5); R ₅ and R ₆ represent independently and can also be substituted A hydrocarbon group with 1 to 6 carbon atoms; n5 and n6 each independently represent an integer from 0 to 4; when there are multiple R5s, multiple _R5s may be the same or different _; when there are multiple _R6s , multiple _R6s Can be the same or different; * means atomic bond; [化5]

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom, or a hydrocarbon group with 1 to 6 carbon atoms that may also be substituted by a halogen atom; * represents an atomic bond; in formula (5), R ₉ and R ₁₀ each independently represent an alkylene group having 1 to 6 carbon atoms which may also be substituted or an arylylene group having 6 to 10 carbon atoms which may also be substituted; * represents an atomic bond. [5] The photosensitive resin composition as in [3] or [4], wherein Ar ₁ in the formula (1) and Ar ₃ in the formula (2) are divalent organic compounds represented by the following formula (6) base, [Chem. 6]

In formula (6), Z ₃ represents ether bond, ester bond, amide bond, urethane bond or urea bond, Z ₄ represents direct bond, ester bond or amide bond; Z ₅ represents direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond; m2 represents an integer from 0 to ₁ ; R11 represents a direct bond, or it can also be substituted by a hydroxyl group An alkylene group having 2 to 6 carbon atoms, R ₁₂ represents a hydrogen atom or a methyl group; * represents an atomic bond. [6] The photosensitive resin composition according to [5], wherein Z ₃ and Z ₄ in the formula (6) are ester bonds. [7] The photosensitive resin composition according to [5] or [6], wherein R ₁₁ in the formula (6) is 1,2-ethylene. [8] The photosensitive resin composition according to any one of [1] to [7], which further contains a photoradical polymerization initiator. [9] The photosensitive resin composition according to any one of [1] to [8], which further contains a crosslinkable compound. [10] The photosensitive resin composition according to any one of [1] to [9], which is used for forming an insulating film. [11] The photosensitive resin composition according to any one of [1] to [10], which is a negative photosensitive resin composition. [12] A resin film, which is a calcined product of the coating film of the photosensitive resin composition according to any one of [1] to [11]. [13] The resin film as in [12] is an insulating film. [14] A photoresist film comprising: a base film; a photosensitive resin layer formed of the photosensitive resin composition according to any one of [1] to [11]; and a cover film. [15] A method of manufacturing a substrate with a hardened relief pattern, comprising the following steps: (1) Coating the photosensitive resin composition according to any one of [1] to [11] on the substrate, and coating the photosensitive resin (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) subjecting the relief pattern to heat treatment to form Hardened undulating pattern. [16] The method for producing a substrate with a cured relief pattern according to [15], wherein the developer used for the development is an organic solvent. [17] A substrate with a hardened relief pattern manufactured using the method for manufacturing a substrate with a hardened relief pattern as described in [15] or [16]. [18] A semiconductor device comprising a semiconductor element and a cured film provided on or under the semiconductor element, the cured film being formed of the photosensitive resin composition according to any one of [1] to [11] Undulating pattern. (Effect of Invention)

According to the present invention, it is possible to obtain a photosensitive resin composition that can be developed with an organic solvent, and the obtained cured film has a low dielectric tangent and a high tensile elongation, a resin film obtained from the composition, and a film using the composition. Photoresist film, manufacturing method of substrate with cured relief pattern, substrate with cured relief pattern, and semiconductor device with cured relief pattern.

(Photosensitive resin composition) The photosensitive resin composition of the present invention contains at least a reaction product and a solvent, and further contains other components as necessary.

＜Reaction product＞ The reaction product is a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings. In terms of constituents, the reaction product contains an aromatic diamine compound having a photopolymerizable group, a tetracarboxylic acid derivative having three or more aromatic rings, and may also contain other diamine compounds, and other Tetracarboxylic acid derivatives are used as constituents. Reaction products, for example: polyamic acid, or polyimide obtained by dehydrating and ring-closing polyamic acid.

Since the reaction product contains an aromatic diamine compound having a photopolymerizable group as a constituent, photosensitivity can be imparted to a resin composition containing the reaction product. The reaction product contains an aromatic diamine compound and a tetracarboxylic acid derivative having three or more aromatic rings as constituents, and the obtained cured film can obtain low dielectric tangent and high tensile elongation.

In the aromatic diamine compound having a photopolymerizable group, two amine groups may be bonded to one aromatic ring, or may be bonded to two aromatic rings respectively. As an aromatic ring, an aromatic hydrocarbon ring, an aromatic heterocyclic ring, etc. are mentioned. Moreover, an aromatic diamine compound may have the aromatic ring to which an amine group is not bonded.

Photopolymerizable groups, for example: radical polymerizable groups, cationic polymerizable groups, anionic polymerizable groups. Among these, a radically polymerizable group is preferable. Radical polymerizable groups, such as: acryl, methacryl, propylene ether, vinyl ether, vinyl, etc.

In the reaction product, if the constituent components include an aromatic diamine compound having three or more aromatic rings other than an aromatic diamine compound having a photopolymerizable group, it is considered that the obtained cured film is more effective. It is more ideal in terms of low dielectric tangent and higher tensile elongation.

The number of aromatic rings in the aromatic diamine compound which has 3 or more aromatic rings is not specifically limited if it is 3 or more, For example, 4 or more may be sufficient. The upper limit of the number of aromatic rings is not particularly limited, and may be, for example, 8 or less, or 6 or less.

For the counting method of aromatic rings in "more than 3 aromatic rings", such as polycyclic aromatic rings formed by condensation of more than 2 aromatic rings of naphthalene ring and anthracene ring, it is calculated as 1 aromatic ring . Therefore, the naphthalene ring counts as one aromatic ring. The biphenyl ring is not a condensed ring, so it is calculated as two aromatic rings. In addition, the perylene ring is regarded as a structure in which two naphthalene rings are bonded, and it is calculated as two aromatic rings. As an aromatic ring, an aromatic hydrocarbon ring, an aromatic heterocyclic ring, etc. are mentioned.

Tetracarboxylic acid derivatives in "tetracarboxylic acid derivatives", such as tetracarboxylic dianhydrides, tetracarboxylic acid dihalides, tetracarboxylic dialkyl esters, and tetracarboxylic dialkyl dihalides, especially tetracarboxylic acid dihalides. Carboxylic dianhydride is preferred.

The derivative of tetracarboxylic acid having three or more aromatic rings is preferably an aromatic tetracarboxylic acid derivative having three or more aromatic rings. Aromatic tetracarboxylic acid refers to a compound in which a total of 4 carboxyl groups are bonded to the same or different aromatic rings.

The number of aromatic rings in the tetracarboxylic acid derivative having 3 or more aromatic rings is not particularly limited as long as it is 3 or more, for example, it may be 4 or more. The upper limit of the number of aromatic rings is not particularly limited, for example: 8 or less, or 6 or less.

The ratio of the aromatic diamine compound having a photopolymerizable group to all the diamine compounds constituting the reaction product is not particularly limited. From the viewpoint of obtaining sufficient photosensitivity, 10-100 mol % is ideal, and 50-100 mol % % is more ideal. The ratio of the aromatic tetracarboxylic acid derivative having 3 or more aromatic rings to all the tetracarboxylic acid derivatives constituting the reaction product is not particularly limited, but it is 20 to 100 moles in consideration of the ideal effect of the present invention. % is more ideal, 50~100 mole % is more ideal.

The reaction product is preferably polyamic acid or polyimide obtained by dehydrating and ring-closing polyamic acid. From the viewpoint of obtaining a finer relief pattern, polyimide obtained by dehydrating and ring-closing polyamic acid is more preferable. Here, the imidization rate of polyimide does not need to be 100%. The imidization rate may be, for example, 90% or more, 95% or more, or 98% or more.

式(1)中，Ar ₁表示具有光聚合性基及芳香族環之2價有機基，Ar ₂表示具有3個以上之芳香族環之4價有機基。 [化8]

式(2)中，Ar ₃表示具有光聚合性基及芳香族環之2價有機基，Ar ₄表示具有3個以上之芳香族環之4價有機基。 The polyamic acid preferably has at least a structural unit represented by the following formula (1). The polyimide preferably has at least a structural unit represented by the following formula (2). [chemical 7]

In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₂ represents a tetravalent organic group having three or more aromatic rings. [chemical 8]

In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having three or more aromatic rings.

<<Ar ₁ and Ar ₃ >> Ar ₁ and Ar ₃ are divalent organic groups having a photopolymerizable group and an aromatic ring, and are not particularly limited as long as they can exhibit the effect of the present invention. Also, the divalent organic group having a photopolymerizable group and an aromatic ring is a residue obtained by removing two amine groups from an aromatic diamine compound having a photopolymerizable group. Photopolymerizable group, for example: aforementioned photopolymerizable group.

式(6)中，Z ₃表示醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)或脲鍵(-NHCONH-)，Z ₄表示直接鍵結、酯鍵(-COO-)或醯胺鍵(-NHCO-)。Z ₅表示直接鍵結、醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)、脲鍵(-NHCONH-)、硫醚鍵(-S-)或磺醯基鍵(-SO ₂-)。m2表示0至1之整數。R ₁₁表示直接鍵結、或亦可被羥基取代之碳原子數2至6之伸烷基，R ₁₂表示氫原子或甲基。＊表示原子鍵。 Ar ₁ and Ar ₃ are preferably divalent organic groups represented by the following formula (6). [chemical 9]

In formula (6), Z ₃ represents an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a carbamate bond (-NHCOO-) or a urea bond (-NHCONH -), Z ₄ represents a direct bond, an ester bond (-COO-) or an amide bond (-NHCO-). Z ₅ means direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), urethane bond (-NHCOO-), urea bond (-NHCONH-) , a thioether bond (-S-) or a sulfonyl bond (-SO ₂ -). m2 represents an integer of 0 to 1. R ₁₁ represents a direct bond or an alkylene group having 2 to 6 carbon atoms which may be substituted by a hydroxyl group, and R ₁₂ represents a hydrogen atom or a methyl group. * Indicates an atomic bond.

An alkylene group with 2 to 6 carbon atoms that can also be substituted by a hydroxyl group, such as: 1,1-ethylene, 1,2-ethylene, 1,2-propylidene, 1,3-propylidene , 1,4-butyl, 1,2-butyl, 2,3-butyl, 1,2-pentyl, 2,4-pentyl, 1,2-hexyl, 1, 2-cyclopropyl, 1,2-cyclobutyl, 1,3-cyclobutyl, 1,2-cyclopentyl, 1,2-cyclohexyl, at least some of these hydrogen atoms have An alkylene group substituted by a hydroxyl group (for example: 2-hydroxy-1,3-propylidene group), etc.

Z ₃ is preferably an ester bond. Z ₄ is preferably an ester bond. R ₁₁ is preferably 1,2-ethylene.

式中，＊表示原子鍵。2個之原子鍵例如相對於具有光聚合性基之取代基位在間位。 The divalent organic group represented by formula (6) is, for example: the following divalent organic group. [chemical 10]

In the formula, * represents an atomic bond. The two atomic bonds are, for example, at the meta position with respect to the substituent having a photopolymerizable group.

式(3)中，X ₁及X ₂各自獨立地表示直接鍵結、醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)、脲鍵(-NHCONH-)、硫醚鍵(-S-)或磺醯基鍵(-SO ₂-)。R ₁及R ₂各自獨立地表示亦可經取代之碳原子數1至6之烷基。Y表示下式(3-1)或(3-2)表示之2價有機基。n1及n2各自獨立地表示0至3之整數。R ₁有多個時，多個R ₁可相同也可不同。R ₂有多個時，多個R ₂可相同也可不同。＊表示原子鍵。 <<Ar ₂ and Ar ₄ >> Ar ₂ in formula (1) and Ar ₄ in formula (2) are not particularly special as long as they are tetravalent organic groups having three or more aromatic rings and exerting the effect of the present invention. Limitations, from the viewpoint of ideally obtaining the effects of the present invention, are preferably divalent organic groups represented by the following formula (3). [chemical 11]

In formula (3), X ₁ and X ₂ each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond ( -NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y represents a divalent organic group represented by the following formula (3-1) or (3-2). n1 and n2 each independently represent the integer of 0-3. When there are multiple R _1s , the multiple R _1s may be the same or different. When there are multiple R _2s , the multiple R _2s may be the same or different. * Indicates an atomic bond.

An alkyl group with ₁ to 6 carbon atoms that may also be substituted in R1 and R2, for example: an alkyl group with ₁ to 6 carbon atoms. An alkyl group with 1 to 6 carbon atoms, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. In the present specification, the alkyl group may be linear, branched, or cyclic, or may be a combination of two or more thereof, unless the structure is particularly mentioned. Substituents in alkyl groups with 1 to 6 carbon atoms that may also be substituted, such as: halogen atom, hydroxyl, mercapto, carboxyl, cyano, formyl, haloformyl, sulfo, amino, nitro , nitroso, pendant oxy, pendant thio, alkoxy with 1 to 6 carbon atoms, etc. Also, "1 to 6 carbon atoms" in "an optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms of the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

式(3-1)中，Z ₁表示直接鍵結、醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)、脲鍵(-NHCONH-)、硫醚鍵(-S-)或磺醯基鍵(-SO ₂-)。R ₃及R ₄各自獨立地表示亦可經取代之碳原子數1至6之烴基。m1表示0至3之整數。n3及n4各自獨立地表示0至4之整數。Z ₁有多個時，多個Z ₁可相同也可不同。n4有多個時，多個n4可相同也可不同。R ₃有多個時，多個R ₃可相同也可不同。R ₄有多個時，多個R ₄可相同也可不同。＊表示原子鍵。 式(3-2)中，Z ₂表示下式(4)或(5)表示之2價有機基。R ₅及R ₆各自獨立地表示亦可經取代之碳原子數1至6之烴基。n5及n6各自獨立地表示0至4之整數。R ₅有多個時，多個R ₅可相同也可不同。R ₆有多個時，多個R ₆可相同也可不同。＊表示原子鍵。 [chemical 12]

In formula ( _3-1 ), Z1 represents a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a carbamate bond (-NHCOO-) , urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₃ and R ₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m1 represents an integer of 0 to 3. n3 and n4 each independently represent the integer of 0-4. When there are a plurality of Z ₁ s, the plurality of Z ₁ may be the same or different. When there are a plurality of n4, the plurality of n4 may be the same or different. When there are multiple R _3s , the multiple R _3s may be the same or different. When there are a plurality of R ₄ , the plurality of R ₄ may be the same or different. * Indicates an atomic bond. In formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5). R ₅ and R ₆ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n5 and n6 each independently represent the integer of 0-4. When there are a plurality of R ₅ s, the plurality of R ₅ may be the same or different. When there are a plurality of R ₆ , the plurality of R ₆ may be the same or different. * Indicates an atomic bond.

Among R ₃ , R ₄ , R ₅ , and R ₆ , a hydrocarbon group with 1 to 6 carbon atoms that may also be substituted, for example: an alkyl group with 1 to 6 carbon atoms that may also be substituted, or an alkyl group with 1 to 6 carbon atoms that may also be substituted phenyl. Substituents, for example: halogen atom, hydroxyl group, mercapto group, carboxyl group, cyano group, formyl group, haloformyl group, sulfo group, amine group, nitro group, nitroso group, side oxygen group, side sulfur group, number of carbon atoms 1 to 6 alkoxy, etc. Also, "1 to 6 carbon atoms" in the "hydrocarbon group having 1 to 6 carbon atoms which may also be substituted" refers to the number of carbon atoms of the "hydrocarbon group" excluding substituents. Also, the number of substituents is not particularly limited.

Specific examples of alkyl groups with 1 to 6 carbon atoms that may also be substituted among R ₃ , R ₄ , R ₅ and R ₆ , for example: the number of carbon atoms that may also be substituted as exemplified in the description of R ₁ and R ₂ 1 to 6 alkyl groups.

式(4)中，R ₇及R ₈各自獨立地表示氫原子、或也可被鹵素原子取代之碳原子數1至6之烴基。＊表示原子鍵。 式(5)中，R ₉及R ₁₀各自獨立地表示亦可經取代之碳原子數1至6之伸烷基或亦可經取代之碳原子數6至10之伸芳基。＊表示原子鍵。 [chemical 13]

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom. * Indicates an atomic bond. In formula (5), R ₉ and R ₁₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylylene group having 6 to 10 carbon atoms. * Indicates an atomic bond.

C1-6 hydrocarbon groups in _R7 and _R8 which may also be substituted by halogen atoms, for example: alkyl groups with 1-6 carbon atoms, halogenated alkyl groups with 1-6 carbon atoms, phenyl, halogenated Phenyl, etc. An alkyl group with 1 to 6 carbon atoms, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. Halogen atom in a halogenated alkyl group having 1 to 6 carbon atoms, for example: fluorine atom, chlorine atom, bromine atom, iodine atom. The halogenation of the halogenated alkyl group having 1 to 6 carbon atoms and the halogenated phenyl group may be part or all.

Substituents in C1-C6 alkylene groups in _R9 and _R10 which may also be substituted, for example: halogen atom, hydroxyl, mercapto, carboxyl, cyano, formyl, haloformyl, Sulfo group, amino group, nitro group, nitroso group, pendant oxy group, pendant thio group, alkoxy group with 1 to 6 carbon atoms, etc. An alkylene group having 1 to 6 carbon atoms that may also be substituted, for example: an alkylene group having 1 to 6 carbon atoms, a halogenated alkylene group having 1 to 6 carbon atoms, and the like. An alkylene group having 1 to 6 carbon atoms, such as methylene, ethylene, propylidene, butylene, etc. Also, "1 to 6 carbon atoms" in "an alkylene group having 1 to 6 carbon atoms which may also be substituted" means the number of carbon atoms of the "alkylene group" excluding the substituent. Also, the number of substituents is not particularly limited.

Substituents in _R9 and R10 may also be substituted aryl groups with 6 to ₁₀ carbon atoms, for example: halogen atoms, alkyl groups with 1 to 6 carbon atoms that may also be halogenated, and may also be substituted A halogenated alkoxy group having 1 to 6 carbon atoms, etc. Moreover, halogenation may be partial or all. Arylylene, for example: phenylene, naphthyl, etc. Also, "6 to 10 carbon atoms" in the "arylylene group having 6 to 10 carbon atoms which may also be substituted" means the number of carbon atoms of the "arylylene group" excluding substituents. Also, the number of substituents is not particularly limited.

式中，＊表示原子鍵。 The divalent organic group represented by formula (4), for example: the divalent organic group represented by the following formula. [chemical 14]

In the formula, * represents an atomic bond.

式中，R ₁₃~R ₁₅各自獨立地表示鹵素原子、也可被鹵素原子取代之碳原子數1至6之烷基、或也可被鹵素原子取代之碳原子數1至6之烷氧基。n13表示0至5之整數。n14及n15各自獨立地表示0至4之整數。R ₁₃有多個時，多個R ₁₃可相同也可不同。R ₁₄有多個時，多個R ₁₄可相同也可不同。R ₁₅有多個時，多個R ₁₅可相同也可不同。＊表示原子鍵。 The divalent organic group represented by formula (5), for example: the divalent organic group represented by the following formula. [chemical 15]

In the formula, R ₁₃ to R ₁₅ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may also be substituted by a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may also be substituted by a halogen atom . n13 represents an integer of 0 to 5. n14 and n15 each independently represent the integer of 0-4. When there are multiple R _13s , the multiple R _13s may be the same or different. When there are multiple R _14s , the multiple R _14s may be the same or different. When there are multiple R _15s , the multiple R _15s may be the same or different. * Indicates an atomic bond.

Specific examples of alkyl groups with 1 to 6 carbon atoms that may also be substituted by halogen atoms in R ₁₃ to R ₁₅ are, for example: alkyl groups with 1 to 6 carbon atoms, halogenated alkyl groups with 1 to 6 carbon atoms. An alkyl group with 1 to 6 carbon atoms, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl, etc. Halogen atom in a halogenated alkyl group having 1 to 6 carbon atoms, for example: fluorine atom, chlorine atom, bromine atom, iodine atom. The halogenation of the halogenated alkyl group having 1 to 6 carbon atoms may be partially or completely. Specific examples of an alkoxy group with 1 to 6 carbon atoms that may also be substituted by a halogen atom in R ₁₃ to R ₁₅ include an alkyl group with 1 to 6 carbon atoms that may also be substituted by a halogen atom. Oxygen.

[化17]

式中，＊表示原子鍵。 Ar ₂ and Ar ₄ are, for example, a tetravalent organic group represented by the following formula. [chemical 16]

[chemical 17]

In the formula, * represents an atomic bond.

式(1’)中，Ar _1’表示具有光聚合性基及芳香族環之2價有機基或具有光聚合性基及芳香族環之2價有機基以外之2價有機基，Ar _2’表示具有3個以上之芳香族環之4價有機基或不具有3個以上之芳香族環之4價有機基。惟Ar _1’為具有光聚合性基及芳香族環之2價有機基且Ar _2’為具有3個以上之芳香族環之4價有機基之情形除外。 [化19]

式(2’)中，Ar _3’表示具有光聚合性基及芳香族環之2價有機基或具有光聚合性基及芳香族環之2價有機基以外之2價有機基，Ar _4’表示具有3個以上之芳香族環之4價有機基或不具有3個以上之芳香族環之4價有機基。惟Ar _3’為具有光聚合性基及芳香族環之2價有機基且Ar _4’為具有3個以上之芳香族環之4價有機基之情形除外。 <Other structural units> The polyamic acid may have other structural units than the structural unit represented by formula (1). Other structural units, for example: the structural unit represented by the following formula (1'). Polyimide may have other structural units other than the structural unit represented by formula (2). Other structural units, for example: the structural unit represented by the following formula (2'). [chemical 18]

In formula (1'), Ar _1' represents a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' Represents a tetravalent organic group having three or more aromatic rings or a tetravalent organic group not having three or more aromatic rings. Except for the case where Ar _1' is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _2' is a tetravalent organic group having three or more aromatic rings. [chemical 19]

In formula (2'), Ar _3' represents a divalent organic group having a photopolymerizable group and an aromatic ring or a divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' Represents a tetravalent organic group having three or more aromatic rings or a tetravalent organic group not having three or more aromatic rings. Except for the case where Ar _3' is a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' is a tetravalent organic group having three or more aromatic rings.

Combinations of Ar _1' and Ar _2' include combinations of (i) to (iii) below. (i): Ar _1' represents a combination of a divalent organic group having a photopolymerizable group and an aromatic ring and Ar _2' represents a tetravalent organic group having no more than three aromatic rings (ii): Ar _1' represents A divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, Ar _2' represents a combination (iii) of a 4-valent organic group that does not have more than three aromatic rings: Ar _1' represents a photosensitive A divalent organic group other than a polymerizable group and a divalent organic group of an aromatic ring, Ar _2' represents a combination of a tetravalent organic group having three or more aromatic rings

Combinations of Ar _3' and Ar _4' include combinations of (iv) to (vi) below. (iv): Ar _3' represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar _4' represents a combination of a tetravalent organic group not having three or more aromatic rings (v): Ar _3' represents A divalent organic group other than a divalent organic group having a photopolymerizable group and an aromatic ring, Ar _4' represents a combination (vi) of a 4-valent organic group that does not have more than 3 aromatic rings: Ar _3' represents a photosensitive A divalent organic group other than a polymerizable group and a divalent organic group of an aromatic ring, Ar _4' represents a combination of a tetravalent organic group having three or more aromatic rings

式(13)中，X ₂₁及X ₂₂各自獨立地表示直接鍵結、醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)、脲鍵(-NHCONH-)、硫醚鍵(-S-)或磺醯基鍵(-SO ₂-)。R ₂₁及R ₂₂各自獨立地表示亦可經取代之碳原子數1至6之烷基。Y ₂₀表示下式(13-1)或(13-2)表示之2價有機基。n21及n22各自獨立地表示0至4之整數。R ₂₁有多個時，多個R ₂₁可相同也可不同。R ₂₂有多個時，多個R ₂₂可相同也可不同。＊表示原子鍵。 <<Ar _1' and Ar _3' >> Ar _1' and Ar _3' are divalent organic groups with photopolymerizable groups and aromatic rings, for example: Ar ₁ and Ar ₃ are photopolymerizable A divalent organic group of a group and an aromatic ring. The divalent organic groups other than the divalent organic groups having a photopolymerizable group and an aromatic ring in Ar _1' and Ar _3' are not particularly limited. In consideration of obtaining a lower dielectric tangent and a higher tensile strength in the obtained cured film From the viewpoint of elongation, a divalent organic group having three or more aromatic rings is preferable. The divalent organic group having three or more aromatic rings is not particularly limited, but is preferably a divalent organic group represented by the following formula (13). [chemical 20]

In formula (13), X ₂₁ and X ₂₂ each independently represent a direct bond, an ether bond (-O-), an ester bond (-COO-), an amide bond (-NHCO-), a urethane bond ( -NHCOO-), urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₂₁ and R ₂₂ each independently represent an optionally substituted alkyl group having 1 to 6 carbon atoms. Y ₂₀ represents a divalent organic group represented by the following formula (13-1) or (13-2). n21 and n22 each independently represent the integer of 0-4. When there are multiple R _21s , the multiple R _21s may be the same or different. When there are multiple R _22s , the multiple R _22s may be the same or different. * Indicates an atomic bond.

Specific examples of the alkyl group having 1 to 6 carbon atoms which may also be substituted in R ₂₁ and R ₂₂ include the alkyl group having 1 to 6 carbon atoms which may also be substituted as exemplified in the description of R ₁ and R ₂ base. Also, "1 to 6 carbon atoms" in "an optionally substituted alkyl group having 1 to 6 carbon atoms" refers to the number of carbon atoms of the "alkyl group" excluding substituents. Also, the number of substituents is not particularly limited.

式(13-1)中，Z ₂₁表示直接鍵結、醚鍵(-O-)、酯鍵(-COO-)、醯胺鍵(-NHCO-)、胺甲酸酯鍵(-NHCOO-)、脲鍵(-NHCONH-)、硫醚鍵(-S-)或磺醯基鍵(-SO ₂-)。R ₂₃及R ₂₄各自獨立地表示亦可經取代之碳原子數1至6之烴基。m21表示0至3之整數。n23及n24各自獨立地表示0至4之整數。Z ₂₁有多個時，多個Z ₂₁可相同也可不同。n24有多個時，多個n24可相同也可不同。R ₂₃有多個時，多個R ₂₃可相同也可不同。R ₂₄有多個時，多個R ₂₄可相同也可不同。＊表示原子鍵。 式(13-2)中，Z ₂₂表示下式(14)或(15)表示之2價有機基。R ₂₅及R ₂₆各自獨立地表示亦可經取代之碳原子數1至6之烴基。n25及n26各自獨立地表示0至4之整數。R ₂₅有多個時，多個R ₂₅可相同也可不同。R ₂₆有多個時，多個R ₂₆可相同也可不同。＊表示原子鍵。 [chem 21]

In formula (13-1), Z ₂₁ represents direct bond, ether bond (-O-), ester bond (-COO-), amide bond (-NHCO-), carbamate bond (-NHCOO-) , urea bond (-NHCONH-), thioether bond (-S-) or sulfonyl bond (-SO ₂ -). R ₂₃ and R ₂₄ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. m21 represents an integer of 0 to 3. n23 and n24 each independently represent the integer of 0-4. When there are multiple Z _21s , the multiple Z _21s may be the same or different. When there are a plurality of n24, the plurality of n24 may be the same or different. When there are multiple R _23s , the multiple R _23s may be the same or different. When there are multiple R _24s , the multiple R _24s may be the same or different. * Indicates an atomic bond. In formula (13-2), Z ₂₂ represents a divalent organic group represented by the following formula (14) or (15). R ₂₅ and R ₂₆ each independently represent an optionally substituted hydrocarbon group having 1 to 6 carbon atoms. n25 and n26 each independently represent the integer of 0-4. When there are multiple R _25s , the multiple R _25s may be the same or different. When there are multiple R _26s , the multiple R _26s may be the same or different. * Indicates an atomic bond.

Specific examples of hydrocarbon groups with 1 to 6 carbon atoms that may be substituted among R ₂₃ , R ₂₄ , R ₂₅ , and R ₂₆ include those exemplified in the description of R ₃ , R ₄ , R ₅ , and R ₆ A hydrocarbon group having 1 to 6 carbon atoms which may be substituted. Also, "1 to 6 carbon atoms" in the "hydrocarbon group having 1 to 6 carbon atoms which may also be substituted" refers to the number of carbon atoms of the "hydrocarbon group" excluding substituents. Also, the number of substituents is not particularly limited.

Specific examples of alkyl groups with 1 to 6 carbon atoms that may also be substituted among R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ , for example: the number of carbon atoms that may also be substituted as exemplified in the descriptions of R ₁ and R ₂ 1 to 6 alkyl groups.

式(14)中，R ₂₇及R ₂₈各自獨立地表示氫原子、或也可被鹵素原子取代之碳原子數1至6之烴基。＊表示原子鍵。 式(15)中，R ₂₉及R ₃₀各自獨立地表示亦可經取代之碳原子數1至6之伸烷基或亦可經取代之碳原子數6至10之伸芳基。＊表示原子鍵。 [chem 22]

In formula (14), R ₂₇ and R ₂₈ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted by a halogen atom. * Indicates an atomic bond. In formula (15), R ₂₉ and R ₃₀ each independently represent an optionally substituted alkylene group having 1 to 6 carbon atoms or an optionally substituted arylylene group having 6 to 10 carbon atoms. * Indicates an atomic bond.

Specific examples of hydrocarbon groups with 1 to 6 carbon atoms that may also be substituted by halogen atoms in R ₂₇ and R ₂₈ include C 1 to 6 hydrocarbon groups that may also be substituted by halogen atoms as exemplified in the description of R ₇ and R ₈ The hydrocarbon group.

Specific examples of the alkylene group having 1 to 6 carbon atoms that may also be substituted in R ₂₉ and R ₃₀ include the alkylene group having 1 to 6 carbon atoms that may also be substituted as exemplified in the description of R ₉ and R ₁₀ alkyl. Also, "1 to 6 carbon atoms" in "an alkylene group having 1 to 6 carbon atoms which may also be substituted" refers to the number of carbon atoms of the "alkylene group" excluding substituents. Also, the number of substituents is not particularly limited.

Specific examples of the aryl group with 6 to 10 carbon atoms that may also be substituted in R ₂₉ and R ₃₀ include the arylylene group with 6 to 10 carbon atoms that may also be substituted as exemplified in the description of R ₉ and R ₁₀ Aryl. In addition, "6 to 10 carbon atoms" in the "arylylene group having 6 to 10 carbon atoms which may also be substituted" means the number of carbon atoms of the "arylylene group" excluding substituents. Also, the number of substituents is not particularly limited.

式中，＊表示原子鍵。 The divalent organic group represented by formula (14), for example: the divalent organic group represented by the following formula. [chem 23]

In the formula, * represents an atomic bond.

式中，R ₃₃~R ₃₅各自獨立地表示鹵素原子、也可被鹵素原子取代之碳原子數1至6之烷基、或也可被鹵素原子取代之碳原子數1至6之烷氧基。n33表示0至5之整數。n34及n35各自獨立地表示0至4之整數。R ₃₃有多個時，多個R ₃₃可相同也可不同。R ₃₄有多個時，多個R ₃₄可相同也可不同。R ₃₅有多個時，多個R ₃₅可相同也可不同。＊表示原子鍵。 The divalent organic group represented by formula (15), for example: the divalent organic group represented by the following formula. [chem 24]

In the formula, R ₃₃ to R ₃₅ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms which may also be substituted by a halogen atom, or an alkoxy group having 1 to 6 carbon atoms which may also be substituted by a halogen atom . n33 represents an integer of 0 to 5. n34 and n35 each independently represent the integer of 0-4. When there are multiple R _33s , the multiple R _33s may be the same or different. When there are multiple _R34s , the multiple _R34s may be the same or different. When there are multiple _R35s , the multiple _R35s may be the same or different. * Indicates an atomic bond.

Specific examples of alkyl groups with 1 to 6 carbon atoms that may also be substituted by halogen atoms in R ₃₃ to R ₃₅ include C 1 to 6 alkyl groups that may also be substituted by halogen atoms as exemplified in the description of R ₁₃ to R ₁₅ . 6 alkyl. Specific examples of an alkoxy group with 1 to 6 carbon atoms that may also be substituted by a halogen atom in R ₃₃ to R ₃₅ include an alkyl group with 1 to 6 carbon atoms that may also be substituted by a halogen atom. Oxygen.

[化26]

式中，＊表示原子鍵。 Ar _1' and Ar _3' are, for example, a divalent organic group represented by the following formula. [chem 25]

[chem 26]

In the formula, * represents an atomic bond.

式中，＊表示原子鍵。 Other Ar _1' and Ar _3' are, for example, a divalent organic group represented by the following formula. [chem 27]

In the formula, * represents an atomic bond.

[化29]

式中，＊表示原子鍵。 <<Ar _2' and Ar _4' >>Ar _2' and Ar _4' are tetravalent organic groups having 3 or more aromatic rings, for example: Ar ₂ and Ar ₄ have 3 or more aromatic rings A tetravalent organic group of an aromatic ring. Quaternary organic groups that do not have more than 3 aromatic rings in Ar _2' and Ar _4' , for example: 4-valent organic groups with 1 or 2 aromatic rings or 4-valent organic groups without aromatic rings Organic based. A tetravalent organic group having one or two aromatic rings is derived from, for example, an aromatic tetracarboxylic dianhydride derivative. Furthermore, the tetravalent organic group not having an aromatic ring is derived from, for example, an aliphatic tetracarboxylic anhydride derivative. Such a 4-valent organic group is not particularly limited, for example: the following 4-valent organic group, etc. [chem 28]

[chem 29]

In the formula, * represents an atomic bond.

The proportion of the structural unit represented by formula (1) in all structural units of polyamide acid is not particularly limited, and considering the viewpoint of obtaining sufficient photosensitivity, it is more ideally 10~100 mole%, and more preferably 50~100 mole%. . In addition, the structural unit is also a repeating unit. When the polyamic acid has a structural unit represented by the formula (1'), the ratio of the structural unit represented by the formula (1') in all structural units of the polyamic acid is not particularly limited, and is preferably 1 to 90 mol%. , 1~50 mol% is more ideal.

When the imidization ratio of the polyimide is not 100%, the polyimide may have a structural unit represented by the formula (1) in addition to the structural unit represented by the formula (2). The total ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in all structural units of polyimide is not particularly limited, but it is 10 to 100 mole % in consideration of obtaining sufficient photosensitivity More ideal, 50~100 mole% is more ideal. When the polyimide has at least any one of the structural unit represented by the formula (1') and the structural unit represented by the formula (2'), the structure represented by the formula (1') in all the structural units of the polyimide The ratio of the unit to the total of the structural units represented by formula (2') is not particularly limited, and is preferably 1-90 mol%, more preferably 1-50 mol%.

The weight average molecular weight of the reaction product is not particularly limited, and the weight average molecular weight measured in terms of polystyrene by gel permeation chromatography (hereinafter referred to as GPC in this specification) is preferably 5,000 to 100,0000, more preferably 7,000 to 50,000 , 10,000~50,000 is better, 10,000~40,000 is especially good.

<Manufacturing method of reaction product> The reaction product is obtained by reacting an aromatic diamine compound having a photopolymerizable group, a tetracarboxylic acid derivative having three or more aromatic rings, other diamine compounds, and other tetracarboxylic acid derivatives if necessary .

The production method of the reaction product is not particularly limited, for example, a known method of obtaining polyamic acid or polyimide by reacting a diamine compound with a tetracarboxylic acid derivative. Polyamic acid and polyimide can be synthesized, for example, by a known method described in WO2013/157586.

The reaction product can be produced by, for example, making a diamine component containing an aromatic diamine compound having a photopolymerizable group, and a tetracarboxylic acid derivative component having three or more aromatic rings in a solvent (polycondensation) reaction to proceed.

式[D-1]中，D ¹表示碳原子數1~3之烷基，式[D-2]中，D ²表示碳原子數1~3之烷基，式[D-3]中，D ³表示碳原子數1~4之烷基。 Specific examples of the above-mentioned solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide Amide, N,N-dimethylacrylamide, N,N-dimethylisobutyramide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone. Also, when the solvent solubility of the polymer is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] ~ formula [D- 3] The solvent indicated. [chem 30]

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group with 1 to 3 carbon atoms; in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

These solvents may be used alone or in combination. In addition, even if it is a solvent in which the reaction product does not dissolve, it can mix and use with the said solvent in the range which does not precipitate a reaction product.

When reacting the diamine component and the tetracarboxylic acid derivative component in a solvent, the reaction can be performed at any concentration, but it is preferably 1-50% by mass, more preferably 5-30% by mass. The reaction may be carried out at a high concentration in the initial stage, and a solvent may be added thereafter. During the reaction, the ratio of the total number of moles of the diamine components to the total number of moles of the tetracarboxylic acid derivative components is preferably 0.8 to 1.2. Like the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting reaction product will be.

When reacting the diamine component and the tetracarboxylic acid derivative component, in order to avoid polymerization of the photopolymerizable group, a thermal polymerization inhibitor may also be added to the reaction system. Thermal polymerization inhibitors, such as: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthrene, N-phenylnaphthylamine, ethylenediaminetetraacetic acid , 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1- Nitro-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N -Phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc. The usage amount of the thermal polymerization inhibitor is not particularly limited.

Polyimide is obtained by dehydrating and ring-closing polyamic acid, the reaction product obtained from the above reaction. The method of obtaining polyimide includes thermal imidization by directly heating the solution of polyamic acid obtained from the above reaction, or chemical imidization by adding a catalyst to the solution of polyamic acid. change. The temperature for thermal imidization in the solution is 100~400°C, preferably 120~250°C, preferably while discharging the water generated by the imidization reaction to the outside of the system.

The above-mentioned chemical imidization can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution obtained by the reaction, and stirring at -20~250°C, preferably 0~180°C. The amount of alkaline catalyst is 0.1~30 mole times of amide acid group, preferably 0.2~20 mole times, the amount of acid anhydride is 1~50 mole times of amide acid group, preferably 1.5~ 30 mol times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, triethylamine is not easy to produce polyisoimide which is a by-product, so it is preferable. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, use of acetic anhydride is preferable because it facilitates purification after the reaction. The imidization rate (the ratio of the repeating unit of the closed ring to all the repeating units of the polyimide precursor, also known as the ring closing rate) obtained by chemical imidization can be adjusted by adjusting the amount of catalyst and The reaction temperature and reaction time are controlled.

When recovering the produced imide product from the above-mentioned imidization reaction solution, the reaction solution may be poured into a solvent and precipitated. Solvents used for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butylcytosol, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like. The polymer precipitated by putting into the solvent can be recovered by filtration, and then dried at normal temperature or heated under normal pressure or reduced pressure.

In polyimide, part or all of the repeating units are ring-closed. The imidization rate in polyimide is preferably 20-99%, more preferably 30-99%, more preferably 50-99%.

Polyimides can also be capped. The blocking method is not particularly limited, and for example, a conventionally known method using a monoamine or an acid anhydride can be used.

式[D-1]中，D ¹表示碳原子數1~3之烷基，式[D-2]中，D ²表示碳原子數1~3之烷基，式[D-3]中，D ³表示碳原子數1~4之烷基。 <Solvent> For the solvent contained in the photosensitive resin composition, considering the solubility of the reaction product, it is better to use an organic solvent. Specifically, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N- Dimethylacrylamide, N,N-dimethylisobutyramide, dimethylsulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-ethyl Acyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 2-hydroxyisobutyrate methyl ester, ethyl lactate or the solvents represented by the following formula [D-1] ~ formula [D-3], etc., can be used separately Use or use in combination of 2 or more types. [chem 31]

In formula [D-1], D ¹ represents an alkyl group with 1 to 3 carbon atoms; in formula [D-2], D ² represents an alkyl group with 1 to 3 carbon atoms; in formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms.

The solvent can be in the range of 30 parts by mass to 1500 parts by mass, preferably 100 parts by mass to 1000 parts by mass, depending on the expected coating film thickness and viscosity of the photosensitive resin composition, relative to 100 parts by mass of the reaction product Use within the range.

＜Other ingredients＞ In the embodiment, the photosensitive resin composition may further contain other components other than the reaction product and the solvent. Other ingredients, such as: photoradical polymerization initiator (also called "photoradical initiator"), crosslinking compound (also called "crosslinking agent"), thermosetting agent, other resin components, fillers , sensitizers, adhesion aids, thermal polymerization inhibitors, azole compounds, hindered phenol compounds, etc.

＜＜Initiator for photoradical polymerization＞＞ The photoradical polymerization initiator is not particularly limited as long as it is a compound that absorbs the light source used during photohardening, for example: tert-butyl peroxyisobutyrate, 2,5-dimethyl-2,5- Bis(benzoyldioxy)hexane, 1,4-bis[α-(tert-butyldioxy)-isopropoxy]benzene, di-tert-butyl peroxide, 2,5-bis Methyl-2,5-bis(tert-butyldioxy)hexene hydroperoxide, α-(isopropylphenyl)-isopropyl hydroperoxide, tert-butyl hydroperoxide, 1,1 -Bis(tert-butyldioxy)-3,3,5-trimethylcyclohexane, 4,4-bis(tert-butyldioxy)trimethyl-butyl acetate, cyclohexanone peroxide , 2,2',5,5'-tetrakis(tert-butyl peroxycarbonyl)diphenyl ketone, 3,3',4,4'-tetrakis(tert-butyl peroxycarbonyl)diphenyl ketone , 3,3',4,4'-tetrakis(third amylperoxycarbonyl)diphenyl ketone, 3,3',4,4'-tetrakis(third hexylperoxycarbonyl)diphenylketone, 3,3'-bis(tertiary butylperoxycarbonyl)-4,4'-dicarboxybenzophenone, tertiary butyl peroxybenzoate, di-tertiary butyl diperoxyisophthalic acid Organic peroxides such as formate esters; quinones such as 9,10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, etc.; benzoine Benzoin derivatives such as benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin; 2,2-dimethoxy-1,2-diphenylethan-1-one , 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-{4-(2-hydroxy-2-methyl-propionyl)benzyl}-phenyl]-2 -Methyl-propan-1-one, phenylglyoxalic acid methyl ester, 2-methyl-1-[4-(methylthio)phenyl]-2-?olinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-oxolinophenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4- 𠰌line-4-yl-phenyl)-butan-1-one and other alkyl phenone compounds; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and other acyl phosphine oxide compounds; 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl] -1,2-Octanedione, 1-(O-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] Oxime ester compounds such as acetone.

Photoradical polymerization initiators can be obtained from commercially available products, such as: IRGACURE [registered trademark] 651, TO 184, TO 2959, TO 127, TO 907, TO 369, TO 379EG, TO 819, TO 819DW, TO 1800, TO Same as 1870, same as 784, same as OXE01, same as OXE02, same as OXE03, same as OXE04, same as 250, same as 1173, same as MBF, same as TPO, same as 4265, same as TPO (above, manufactured by BASF), KAYACURE [registered trademark] DETX- S. Same as MBP, same DMBI, same EPA, same OA (above, made by Nippon Kayaku (stock)), VICURE-10, same 55 (above, made by STAUFFER Co.LTD), ESACURE KIP150, same TZT, same 1001, Same as KTO46, same KB1, same KL200, same KS300, same EB3, three 𠯤-PMS, three 𠯤A, three 𠯤B (above, Japan SiberHegner (stock) system), ADEKAOPTOMERN-1717, same N-1414, same N- 1606, ADEKA ARKLS N-1919T, same as NCI-831E, same as NCI-930, same as NCI-730 (above, made by (stock) ADEKA). These photoradical polymerization initiators may be used alone, or may be used in combination of 2 or more types.

The content of the photoradical polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the reaction product, and more preferably 0.5 to 15 parts by mass in consideration of photosensitivity characteristics. When the photoradical polymerization initiator contains 0.1 parts by mass or more with respect to 100 parts by mass of the reaction product, the photosensitivity of the photosensitive resin composition tends to increase; on the other hand, when it contains 20 parts by mass or less, the thickness of the photosensitive resin composition Film sclerosis is easy to improve.

＜＜Cross-linking compound＞＞ In the embodiment, in order to improve the resolution of the relief pattern, a monomer (crosslinkable compound) having a photoradically polymerizable unsaturated bond may be optionally included in the photosensitive resin composition. Such a cross-linking compound is preferably a (meth)acrylic compound that undergoes a radical polymerization reaction due to a photoradical polymerization initiator, and is not particularly limited to the following, but diethylene glycol di(methyl) Acrylates, tetraethylene glycol di(meth)acrylates, ethylene glycol or polyethylene glycol mono- or di(meth)acrylates, propylene glycol or polypropylene glycol mono- or di(meth)acrylates, glycerin Mono, di or tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonane Di(meth)acrylate of alkanediol, di(meth)acrylate of 1,10-decanediol, di(meth)acrylate of neopentyl glycol, cyclohexane di(meth)acrylate Acrylate, di(meth)acrylate of cyclohexane dimethanol, di(meth)acrylate of tricyclodecane dimethanol, di(meth)acrylate of dioxanediol, bisphenol A Mono or di(meth)acrylate, di(meth)acrylate of bisphenol F, di(meth)acrylate of hydrogenated bisphenol A, benzenetrimethacrylate, 9,9-bis[4- (2-Hydroxyethoxy) phenyl] bis (meth) acrylate, ginseng (2-hydroxyethyl) isocyanurate di (meth) acrylate, isocamphoryl (methyl) Acrylates, acrylamide and its derivatives, methacrylamide and its derivatives, trimethylolpropane tri(meth)acrylate, glycerol di- or tri(meth)acrylate, neopentylitol Two, three, or four (meth)acrylates, and compounds such as ethylene oxide or propylene oxide adducts of these compounds, 2-isocyanate ethyl (meth)acrylate or isocyanate-containing (methyl) ) acrylates, and to which methyl ethyl ketoxime, ε-caprolactam, γ-caprolactam, 3,5-dimethylpyrazole, diethyl malonate, ethanol, isopropanol, Compounds of capping agents such as n-butanol and 1-methoxy-2-propanol. Moreover, these compounds may be used individually or in combination of 2 or more types. Moreover, in this specification, (meth)acrylate means acrylate and methacrylate.

The content of the crosslinking compound is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the reaction product.

＜＜Thermohardener＞＞ Thermal hardeners, such as: hexamethoxymethylmelamine, tetramethoxymethyl glycoluril, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetra(methoxymethyl) glycoluril , 1,3,4,6-tetra(butoxymethyl) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril, 1,3-bis(hydroxymethyl)urea, 1 , 1,3,3-tetra(butoxymethyl)urea and 1,1,3,3-tetra(methoxymethyl)urea, etc. The content of the thermosetting agent in the photosensitive resin composition is not particularly limited.

＜＜Packing＞＞ The filler is, for example, an inorganic filler, specifically, a sol of silica, aluminum nitride, boron nitride, zirconia, alumina, or the like. In the photosensitive resin composition, the content of the filler is not particularly limited.

＜＜Other resin components＞＞ In an embodiment, the photosensitive resin composition may further contain resin components other than the reaction product. The photosensitive resin composition may contain resin components, such as polyoxazole, polyoxazole precursor, phenolic resin, polyamide, epoxy resin, siloxane resin, acrylic resin, etc. The content of these resin components is not particularly limited, but is preferably in the range of 0.01 to 20 parts by mass relative to 100 parts by mass of the reaction product.

＜＜Sensitizer＞＞ In the embodiment, a sensitizer can be arbitrarily blended into the photosensitive resin composition in order to improve the photosensitivity. Sensitizers, for example: Micheler's ketone, 4,4'-bis(diethylamino)diphenyl ketone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2 ,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4' -Bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene bis Hydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinyl)benzothiazole, 2-(p-dimethylaminophenylene Vinyl)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3' -Carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3 -Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-? Amyl ester, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl) Benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethyl Aminobenzoyl) styrene, etc. These can be used individually or in combination of multiple types.

The content of the sensitizer is not particularly limited, but is preferably 0.1 parts by mass to 25 parts by mass relative to 100 parts by mass of the reaction product.

＜＜Adhesive Auxiliary＞＞ In the embodiment, in order to improve the adhesion between the film formed by using the photosensitive resin composition and the substrate, an adhesion auxiliary agent may be arbitrarily blended into the photosensitive resin composition. Adhesion aids, such as: γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxy Dimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethoxymethylsilane, 3-(methyl) Acryloxypropyltrimethoxysilane, Dimethoxymethyl-3-N-hexahydropyridylpropylsilane, Diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl)succinimide, N-[3-(triethoxysilyl)propyl]phthalimide, benzophenone-3, 3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl silane coupling agents such as base]propylamide)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propylsuccinic anhydride, N-anilinopropyltrimethoxysilane, and ginseng ( Aluminum-based adhesives such as ethyl acetylacetate) aluminum, ginseng (acetylacetonate) aluminum, ethyl acetylacetate aluminum diisopropionate, etc.

Among these adhesion aids, it is more preferable to use a silane coupling agent from the viewpoint of adhesion.

The content of the adhesion aid is not particularly limited, but is preferably within a range of 0.5 parts by mass to 25 parts by mass relative to 100 parts by mass of the reaction product.

＜＜Thermal polymerization inhibitor＞＞ In the embodiment, especially in order to improve the viscosity of the photosensitive resin composition and the stability of the photosensitivity when it is stored in the state of a solution containing a solvent, a thermal polymerization inhibitor may be arbitrarily blended. Thermal polymerization inhibitors, such as: hydroquinone, 4-methoxyphenol, N-nitrosodiphenylamine, p-tert-butylcatechol, phenanthrene, N-phenylnaphthylamine, ethylenediaminetetraacetic acid , 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-p-cresol, 5-nitroso-8-hydroxyquinoline, 1- Nitro-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N -Phenylhydroxylamine ammonium salt, N-nitroso-N(1-naphthyl)hydroxylamine ammonium salt, etc.

The content of the thermal polymerization inhibitor is not particularly limited, but is preferably in the range of 0.005 parts by mass to 12 parts by mass relative to 100 parts by mass of the reaction product.

＜＜Azole compound＞＞ For example, when using a substrate made of copper or a copper alloy, an azole compound can be arbitrarily blended into the photosensitive resin composition in order to suppress discoloration of the substrate. Azole compounds, such as: 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H- Triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl- 1-(2-Dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H -triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethyl Benzyl)phenyl]-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl -2-Hydroxyphenyl)-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-th Trioctylphenyl)benzotriazole, hydroxyphenylbenzotriazole, tolyltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 4- Carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino- 1H-tetrazole, 1-methyl-1H-tetrazole, etc. Particularly preferred are, for example, tolyltriazole, 5-methyl-1H-benzotriazole, and 4-methyl-1H-benzotriazole. In addition, these azole compounds may be used alone or in mixture of two or more.

The content of the azole compound is not particularly limited, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the reaction product, and more preferably 0.5 to 5 parts by mass from the viewpoint of photosensitivity characteristics. When the content of the azole compound is 0.1 parts by mass or more with respect to 100 parts by mass of the reaction product, when the photosensitive resin composition is formed on copper or copper alloy, discoloration of the surface of copper or copper alloy can be suppressed; on the other hand, 20 Since the light sensitivity is excellent in the case of less than a mass part, it is preferable.

＜＜Hindered phenol compounds＞＞ In an embodiment, in order to suppress discoloration on copper, a hindered phenol compound may be arbitrarily blended into the photosensitive resin composition. Hindered phenol compounds, such as: 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-butyl-hydroquinone, 3-(3,5-di-tert-butyl-4- Octadecyl hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6 -di-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-th tributylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylene bis[3-(3,5-di-tert-butyl-4 -Hydroxyphenyl) propionate], N,N'hexamethylene bis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis(4-ethyl-6-tert-butylphenol), tetrakis[3-(3,5-di tert-butyl-4-hydroxyphenyl) propionate] neopentylthritol ester, ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5 -Trimethyl-2,4,6-paraffin(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-paraffin(3-hydroxy-2,6-dimethyl -4-isopropylbenzyl)-1,3,5-tri-(3-butyl)-2,4,6-(1H,3H,5H)-trione, -3-Hydroxy-2,6-dimethylbenzyl)-1,3,5-three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng( 4-Second-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1, 3,5-Phen[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-tris-2,4,6-(1H, 3H,5H)-triketone, 1,3,5-para[4-triethylmethyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-trione-2, 4,6-(1H,3H,5H)-trione, 1,3,5-paraffin(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-tri 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng(4-tert-butyl-3-hydroxy-2,5,6-trimethylbenzyl) -1,3,5-Three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng (4-tert-butyl-5-ethyl-3-hydroxyl -2,6-Dimethylbenzyl)-1,3,5-tri-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng (4-third Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-trimethalone-2,4,6-(1H,3H,5H)- Triketones, 1,3,5-ginseng (4-tert-butyl-6-ethyl-3-hydroxy-2,5-dimethylbenzyl)-1,3,5-trisalpha-2,4 ,6-(1H,3H,5H)-trione, 1,3,5-paraffin(4-tert-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1 ,3,5-Three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng (4-tert-butyl-3-hydroxy-2-methylbenzyl )-1,3,5-three 𠯤-2,4,6-(1H,3H,5H)-trione, 1,3,5-ginseng (4-tert-butyl-3-hydroxyl-2,5 -Dimethylbenzyl)-1,3,5-tri-(3-butyl-5-2,4,6-(1H,3H,5H)-trione, ‐Ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-trione-2,4,6-(1H,3H,5H)-trione, etc., but not limited thereto. Among them, 1,3,5-para(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris-2,4,6- (1H,3H,5H)-triketones are particularly preferred.

The content of the hindered phenolic compound is not particularly limited, but is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the reaction product, and more preferably 0.5 to 10 parts by mass from the viewpoint of photosensitivity. When the content of the hindered phenol compound is 0.1 parts by mass or more relative to 100 parts by mass of the reaction product, for example, when forming a photosensitive resin composition on copper or copper alloy, it can prevent discoloration and corrosion of copper or copper alloy, and On the one hand, when it is 20 mass parts or less, since the light sensitivity is excellent, it is preferable.

The photosensitive resin composition is suitably used as a negative photosensitive resin composition for producing a cured relief pattern described later.

(resin film) The resin film of the present invention is a calcined product of the coating film of the photosensitive resin composition of the present invention. The coating method can use the conventional method for coating the photosensitive resin composition, for example: the method of coating with a spin coater, a coating rod, a knife coater, a curtain coater, a screen printing machine, etc., and A method of spray coating with a spray coater, etc. For the method of calcination to obtain a calcined product, various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-intensive oven capable of setting a temperature program can be selected. Calcination can be implemented, for example, at 130° C. to 250° C. for 30 minutes to 5 hours. Air can be used as the gas environment during heating and hardening, and inert gases such as nitrogen and argon can also be used. The thickness of the resin film is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm. Resin film, for example: insulating film.

(photoresist film) The photosensitive resin composition of the present invention can be used for photoresist films (so-called dry film resists). A photoresist film has a base film, a photosensitive resin layer (photosensitive resin film) formed of the photosensitive resin composition of the present invention, and a cover film. Usually, a photosensitive resin layer and a cover film are laminated|stacked in this order on a base film.

The photoresist film can be produced by, for example, coating a photosensitive resin composition on a base film, drying it to form a photosensitive resin layer, and laminating a cover film on the photosensitive resin layer. . The coating method can use the method used in the coating of the photosensitive resin composition in the past, for example, the method of coating with a spin coater, a coating bar, a knife coater, a curtain coater, a screen printing machine, etc. can be used, A method of spray coating with a spray coater, etc. Drying method, for example: 1 minute to 1 hour at 20°C~200°C. The thickness of the obtained photosensitive resin layer is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

As the base film, known products can be used, for example, thermoplastic resin films and the like can be used. The thermoplastic resin is, for example, polyester such as polyethylene terephthalate. The thickness of the substrate film is preferably 2 μm to 150 μm. As the cover film, known products can be used, for example, polyethylene film, polypropylene film, etc. can be used. For the surface coating film, it is better to use a film whose adhesive force with the photosensitive resin layer is smaller than that of the base film. The thickness of the surface coating film is ideally 2 μm to 150 μm, more preferably 2 μm to 100 μm, and most preferably 5 μm to 50 μm. The base film and the cover film may be made of the same film material, or different films may be used.

(Manufacturing method of substrate with hardened relief pattern) The manufacturing method of the substrate with hardened relief pattern of the present invention comprises the following steps: (1) coating the photosensitive resin composition of the present invention on a substrate, and forming a photosensitive resin layer (photosensitive resin film) on the substrate, (2) exposing the photosensitive resin layer, (3) developing the exposed photosensitive resin layer to form a relief pattern, and (4) The relief pattern is heat-treated to form a hardened relief pattern.

The following describes each step.

(1) A step of coating the photosensitive resin composition of the present invention on a substrate and forming a photosensitive resin layer on the substrate In this step, the photosensitive resin composition of the present invention is coated on a substrate, and dried if necessary to form a photosensitive resin layer. The coating method can adopt the coating method used from the previous photosensitive resin composition, for example: the method of coating with a spin coater, a coating rod, a knife coater, a curtain coater, a screen printing machine, etc., by spraying A method of spray coating by a coating machine, etc.

The coating film composed of the photosensitive resin composition can be dried if necessary, and the drying method can be, for example, air drying, heat drying using an oven or a hot plate, and vacuum drying. Specifically, when air-drying or heat-drying is performed, the drying can be carried out at 20° C. to 200° C. for 1 minute to 1 hour. According to the above, a photosensitive resin layer can be formed on the substrate.

(2) The step of exposing the photosensitive resin layer In this step, the photosensitive resin layer formed in the above step (1) is exposed using a contact aligner, mirror projection, stepper, etc. Expose with a photomask or a reticle or directly with an ultraviolet light source. Light sources used for exposure, such as g-rays, h-rays, i-rays, ghi line-broadband, and KrF excimer lasers. The exposure amount is preferably 25mJ/cm ² -2000mJ/cm ² .

Afterwards, post-exposure baking (PEB) and/or pre-development baking may be applied in any combination of temperature and time as needed for the purpose of increasing photosensitivity. For the range of baking conditions, the temperature is preferably 50° C. to 200° C., and the time is 10 seconds to 600 seconds. However, as long as the properties of the photosensitive resin composition are not hindered, it is not limited to this range.

(3) The step of developing the exposed photosensitive resin layer to form a relief pattern In this step, the unexposed portion in the exposed photosensitive resin layer is developed and removed. The developing method for developing the photosensitive resin layer after exposure (irradiation) can be selected from conventionally known photoresist developing methods, for example, any one can be selected from spin spraying method, dipping method, dipping method accompanied by ultrasonic treatment, etc. method. Moreover, after image development, rinse may be implemented in order to remove a developing solution. In addition, for the purpose of adjusting the shape of a relief pattern, etc., you may perform post-development baking by the combination of arbitrary temperature and time as needed. The developer used for development should be an organic solvent. Organic solvents, such as: N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, cyclopentanone, cyclohexanone , γ-butyrolactone, α-acetyl-γ-butyrolactone, etc. are preferred. Moreover, two or more kinds of each solvent, for example, several kinds may be used in combination. The eluent used for rinsing should be an organic solvent that can be mixed with the developer and has low solubility for the photosensitive resin composition. Eluents such as methanol, ethanol, isopropanol, ethyl lactate, propylene glycol methyl ether acetate, toluene, xylene, etc. are preferred. Moreover, two or more kinds of each solvent, for example, several kinds may be used in combination.

(4) The step of heat-treating the relief pattern to form a hardened relief pattern In this step, the relief pattern obtained by the above-mentioned development is heated to convert it into a hardened relief pattern. When the reaction product is polyamic acid, thermal imidization is carried out by using this heating, and a hardened relief pattern containing polyimide is obtained. Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature-intensive oven capable of setting a temperature program can be used as the method of heating and hardening. Heating can be carried out at, for example, 130°C to 250°C for 30 minutes to 5 hours. Air can also be used as the gas environment during heating and hardening, and inert gases such as nitrogen and argon can also be used.

The thickness of the hardened relief pattern is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 2 μm to 50 μm.

(semiconductor device) In the embodiment, there is also provided a semiconductor device including a semiconductor element and a cured film provided on or under the semiconductor element. The cured film is a cured relief pattern formed from the photosensitive resin composition of the present invention. The hardened relief pattern, for example, can be obtained through the steps (1)-(4) in the above-mentioned manufacturing method of the substrate with the hardened relief pattern. Furthermore, the present invention can also be applied to a method of manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method of manufacturing a substrate with a hardened relief pattern as a part of the steps. The semiconductor device of the present invention can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film for a semiconductor device having a bump structure by forming a hardened relief pattern, and It is manufactured in combination with known semiconductor device manufacturing methods.

(display device) In an embodiment, there is provided a display device including a display element and a cured film provided on an upper portion of the display element, wherein the cured film is the above-mentioned cured relief pattern. Here, the cured relief pattern may be laminated on the display element in direct contact, or may be laminated with other layers interposed therebetween. For example, the cured film can include surface protection films, insulating films, and planarizing films for TFT (Thin Film Transistor) liquid crystal display elements and color filter elements, and protrusions for MVA (Multi-domain Vertical Alignment) type liquid crystal display devices. , and organic EL (Electro-Luminescence) element cathode partition.

The photosensitive resin composition of the present invention is not only applicable to the above-mentioned semiconductor devices, but also useful in interlayer insulating films of multilayer circuits, surface coating of flexible copper clad laminates, solder resist films, and liquid crystal alignment films. [Example]

The following examples are used to describe the content of the present invention in detail, but the present invention is not limited thereto.

The weight average molecular weight (Mw) shown in the following synthesis examples is the result of measurement by gel permeation chromatography (hereinafter referred to as GPC in this specification). A GPC apparatus (HLC-8320GPC (manufactured by Tosoh Co., Ltd.)) was used for the measurement, and the measurement conditions are as follows. ・Pipe string: Shodex[registered trademark] KD-805/Shodex[registered trademark] KD-803 (manufactured by Showa Denko Co., Ltd.) ・Column temperature: 50°C ・Flow rate: 1mL/min ・Eluent: N,N-dimethylformamide (DMF), lithium bromide monohydrate (30mM)/phosphoric acid (30mM)/tetrahydrofuran (1%) ・Standard sample: polyethylene oxide

The chemical imidization ratios shown in the following synthesis examples are calculated according to the following method. Put 100 mg of polyimide powder into an NMR sample tube (NMR standard sampling tube, φ5 (manufactured by Kusano Science Co., Ltd.)), add deuterated dimethyl sulfide (DMSO-d6, 0.05% TMS (tetramethylsilane ) Mixture) (0.53ml), apply ultrasound to dissolve it completely. This solution was measured for proton NMR at 500 MHz with an NMR measuring apparatus (JNM-ECA500) (manufactured by JEOL Ltd.). The chemical imidization rate is determined by using the protons from the structure that does not change before and after imidization as the standard proton, using the peak cumulative value of this proton, and the peak value from the amide that appears around 9.5ppm~11.0ppm The cumulative value of the proton peak of the NH group is calculated according to the following formula. Chemical imidization rate (%)＝(1-α・x/y)×100 In the above formula, x is the cumulative value of the proton peak from the NH group of amide acid, y is the cumulative value of the peak part of the reference proton, and α is the relative value of the polyamide acid (imidization rate of 0%) relative to the acyl The ratio of the number of standard protons to one NH group proton of an amino acid.

<Synthesis Example 1> Synthesis of polyamic acid (P-1) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 11.00g, 0.05g of 2,6-di-tert-butyl-p-cresol, and 33.14g of N-ethyl-2-pyrrolidone were stirred at room temperature under air to dissolve them, and then 4,4'- Add 21.45g of (4,4'-isopropylidenediphenoxy)diphthalic anhydride and 42.68g of N-ethyl-2-pyrrolidone into the system, stir at room temperature for 1 hour, and then Stirred for 93 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-1), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 22,868. [chem 32]

<Synthesis Example 2> Synthesis of polyamic acid (P-2) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 9.85g, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene 12.84g, 2,6-di-tert-butyl p-cresol 0.04g, and N-ethyl 53.04 g of 2-pyrrolidone was stirred under air at room temperature to dissolve, and 37.25 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and 86.91 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-2), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 25,273. [chem 33]

<Synthesis Example 3> Synthesis of polyamic acid (P-3) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 10.18g, 1,4-bis(4-aminophenoxy)benzene 11.26g, 2,6-di-tert-butyl-p-cresol 0.04g, and N-ethyl-2-pyrrolidone 50.13g in After stirring at room temperature under air to dissolve, 38.49 g of 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, and N-ethyl-2- 89.82 g of pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-3), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 26,998. [chem 34]

<Synthesis Example 4> Synthesis of polyamic acid (P-4) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 13.73g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 9.14g, 2,6-di-tert-butyl p-cresol 0.06g, and N-ethyl- 53.50 g of 2-pyrrolidone was stirred at room temperature under air to dissolve it, and 37.08 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N -86.53 g of ethyl-2-pyrrolidone was added to the system, stirred at room temperature for 2 hours, and then stirred at 50°C for 88 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-4), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 24,973. [chem 35]

<Synthesis Example 5> Synthesis of polyamic acid (P-5) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 9.47g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 14.70g, 2,6-di-tert-butyl p-cresol 0.04g, and N-ethyl- 56.49 g of 2-pyrrolidone was stirred at room temperature under air to dissolve it, and 35.79 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N -83.51 g of ethyl-2-pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 89 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-5), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 27,852. [chem 36]

<Synthesis Example 6> Synthesis of polyamic acid (P-6) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 3.59g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 13.01g, 2,6-di-tert-butyl p-cresol 0.01g, and N-ethyl- 66.47g of 2-pyrrolidone was stirred under air at room temperature to dissolve it, and 23.33g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N -93.33 g of ethyl-2-pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 95 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-6), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 56,737. [chem 37]

<Synthesis Example 7> Synthesis of polyamic acid (P-7) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 1.16g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 16.22g, 2,6-di-tert-butyl p-cresol 0.01g, and N-ethyl- 69.53g of 2-pyrrolidone was stirred at room temperature under air to dissolve it, and 22.62g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N -90.47 g of ethyl-2-pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 95 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-7), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 58,225. [chem 38]

<Synthesis Example 8> Synthesis of polyamic acid (P-8) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 9.71g, 4,4'-bis(4-aminophenoxy)biphenyl 13.54g, 2,6-di-tert-butyl-p-cresol 0.04g, and N-ethyl-2-pyrrolidone 54.34 g Stirred under air at room temperature to dissolve, then 36.72g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N-ethyl- 85.67 g of 2-pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 50°C for 92 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-8), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 33,012. [chem 39]

<Synthesis Example 9> Synthesis of polyamic acid (P-9) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. )6.22g, bis[4-(4-aminophenoxy)phenyl]pyridine 10.18g, 2,6-di-tert-butyl-p-cresol 0.03g, and N-ethyl-2-pyrrolidone 65.70 g was stirred at room temperature under the air to dissolve, and 23.52 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N-ethyl- 94.08 g of 2-pyrrolidone was added to the system, stirred at room temperature for 2 hours, and then stirred at 50°C for 92 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-9), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 31,175. [chemical 40]

<Synthesis Example 10> Synthesis of polyamic acid (P-10) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 6.62g, 9,9-bis[4-(4-aminophenoxy)phenyl] terpene (BPF-AN, manufactured by JFE Chemical Co., Ltd.) 13.34g, and N-ethyl-2-pyrrolidone 79.86 g was stirred at room temperature under air to dissolve, then 25.04 g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, and N-ethyl- 25.14 g of 2-pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 40°C for 42 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-10), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 25,249. [chem 41]

<Synthesis Example 11> Synthesis of polyamic acid (P-11) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 7.94g, bis(4-aminophenyl)terephthalate 10.46g, 4-methoxyphenol 0.05g, and N-ethyl-2-pyrrolidone 87.05g were stirred at room temperature under air, After dissolving it, add 29.98 g of 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride and 58.04 g of N-ethyl-2-pyrrolidone into the system , stirred at room temperature for 3 hours, then stirred at 50°C for 74 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-11), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 29,792. [chem 42]

<Synthesis Example 12> Synthesis of polyamic acid (P-12) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 7.94g, 1,4-phenylene bis(4-aminobenzoate) 10.46g, 4-methoxyphenol 0.05g, and N-ethyl-2-pyrrolidone 87.05g in the air, room Stir warmly to make it dissolve, add 29.98g of 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride and 58.04g of N-ethyl-2-pyrrolidone Into the system, stirred at room temperature for 3 hours, then stirred at 50°C for 74 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-12), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 24,660. [chem 43]

<Synthesis Example 13> Synthesis of polyamic acid (P-13) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 10.95g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 17.01g, 2,6-di-tert-butyl p-cresol 0.05g, and N-ethyl- 112.00 g of 2-pyrrolidone was stirred at room temperature under air to dissolve, and then 32.00 g of hydroquinone diphthalic anhydride (manufactured by HQDA, AIR WATER Co., Ltd.) and 28.00 g of N-ethyl-2-pyrrolidone g was added to the system, stirred at room temperature for 2 hours, and then stirred at 40°C for 39 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-13), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 21,092. [chem 44]

<Synthesis Example 14> Synthesis of polyamic acid (P-14) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 8.63g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 13.41g, 2,6-di-tert-butyl p-cresol 0.04g, and N-ethyl- 88.32g of 2-pyrrolidone was stirred at room temperature under air to dissolve it, and then bis-(1,3-dihydroisobenzofuran-5-carboxylic acid)propane-2 , 37.92g of 2-diylbis(2-methyl-4,1-phenylene) and 51.68g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, then stirred at 40°C 39 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-14), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 16,379. [chem 45]

<Synthesis Example 15> Synthesis of polyamic acid (P-15) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 6.23g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 9.68g, and N-ethyl-2-pyrrolidone 63.64g were stirred at room temperature under air to dissolve Then, 29.09 g of 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl stilbenic anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.), and N-ethyl-2- 41.36 g of pyrrolidone was added to the system, stirred at room temperature for 3 hours, and then stirred at 40°C for 42 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-15), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 24,559. [chem 46]

<Synthesis Example 16> Synthesis of polyamic acid (P-16) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries )5.29g, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 10.36g, 4-methoxyphenol 0.04g, and N-ethyl-2-pyrrolidone 65.87g After stirring at room temperature under the air to dissolve, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl stimulic anhydride (BPF-PA, manufactured by JFE Chemical Co., Ltd.) 24.68 g and 28.23 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 4 hours, and then stirred at 50°C for 26.5 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-16), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 28,330. [chem 47]

<Synthesis Example 17> Synthesis of polyamic acid (P-17) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries )6.181g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 9.60g, 4-methoxyphenol 0.04g, and N-ethyl-2-pyrrolidone 79.65g in air After stirring at room temperature and dissolving, 5-isobenzofuran carboxylic acid, 1,3-dihydro-1,3-dioxy-cyclohexyl-4,1-phenylene ester (BPZ -TME, manufactured by Honshu Chemical Co., Ltd.) and 39.82 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 1 hour, and then stirred at 50° C. for 63 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-17), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 13,550. [chem 48]

<Synthesis Example 18> Synthesis of polyamic acid (P-18) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 8.65g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 13.44g, 4-methoxyphenol 0.053g, and N-ethyl-2-pyrrolidone 105.62g in air After stirring at room temperature and dissolving it, 15.0 g of p - phenylenebis ( trimellitate anhydride) (manufactured by TAHQ, MANAC (stock)) and 4, Add 15.67g of 4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 52.81g of N-ethyl-2-pyrrolidone into the system, and stir at room temperature for 1 hour, Stir at 50°C for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-18), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 36,287. [chem 49]

<Synthesis Example 19> Synthesis of polyamic acid (P-19) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 8.65g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 13.44g, 4-methoxyphenol 0.054g, and N-ethyl-2-pyrrolidone 107.24g in air After stirring at room temperature and dissolving it, 9.0 g of p-phenylenebis (trimellitate anhydride) (manufactured by TAHQ, MANAC (stock)) and 4, Add 22.49g of 4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride and 53.62g of N-ethyl-2-pyrrolidone into the system, and stir at room temperature for 1 hour, Stir at 50°C for 40 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-19), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 34,006. [chemical 50]

<Synthesis Example 20> Synthesis of polyamic acid (P-20) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries, Ltd. ) 7.418g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 11.52g, 4-methoxyphenol 0.047g, and N-ethyl-2-pyrrolidone 126.47g in air After stirring at room temperature and dissolving it, 15.0 g of p-bis(trimellitic acid monoester anhydride) (BP-TME, manufactured by Honshu Chemical Co., Ltd.), 4,4'-(4, Add 13.44g of 4'-isopropylidene diphenoxy)diphthalic anhydride and 63.23g of N-ethyl-2-pyrrolidone into the system, stir at room temperature for 1 hour, then stir at 50°C for 40 hours . The obtained polyamic acid had a repeating unit structure represented by the following (P-20), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 28,962. [Chemical 51]

<Synthesis Example 21> Synthesis of polyamic acid (P-21) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, manufactured by Wako Pure Chemical Industries ) 7.418g, 2,2-bis[4-(4-aminophenoxy)phenyl]propane 11.52g, 4-methoxyphenol 0.047g, and N-ethyl-2-pyrrolidone 126.47g in air After stirring at room temperature and dissolving it, 9.0 g of p-bis(trimellitic acid monoester anhydride) (BP-TME, manufactured by Honshu Chemical Co., Ltd.), 4,4'-(4, Add 19.28g of 4'-isopropylidene diphenoxy)diphthalic anhydride and 63.23g of N-ethyl-2-pyrrolidone into the system, stir at room temperature for 1 hour, then stir at 50°C for 40 hours . The obtained polyamic acid had a repeating unit structure represented by the following (P-21), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 26,182. [Chemical 52]

<Synthesis Example 22> Synthesis of solvent-soluble polyimide (P-22) To 40.21 g of polyamic acid (P-16) obtained in Synthesis Example 16, 80.42 g of N-ethyl-2-pyrrolidone, After stirring 3.66 g of acetic anhydride and 0.61 g of triethylamine at room temperature under air for 30 minutes, it stirred at 60 degreeC for 3 hours. This solution was slowly added to 437.15 g of methanol under stirring, stirred for 10 minutes, and the obtained precipitate was separated and filtered. This precipitate was washed with 874.30 g of methanol, and then dried under reduced pressure at 80° C. to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by the following (P-22). The chemical imidization rate was 95.3%. [Chemical 53]

<Synthesis Example 23> Synthesis of solvent-soluble polyimide (P-23) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries, Ltd. (stock)) 9.51g, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 18.66g, 4-methoxyphenol 0.06g, and N-ethyl-2 - 98.06 g of pyrrolidone was dissolved under air at room temperature by stirring, and 23.99 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4' 7.87 g of -isopropylidene (diphenoxy) diphthalic anhydride and 42.03 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, and then stirred at 50° C. for 24 hours. The weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 29,468. Add 100.00 g of N-ethyl-2-pyrrolidone, 5.51 g of acetic anhydride, and 0.91 g of triethylamine to 50.00 g of the obtained polyamic acid, stir at room temperature for 30 minutes in air, and then stir at 60°C for 3 hours . This solution was slowly added to 547.47 g of methanol under stirring, stirred for 10 minutes, and the obtained precipitate was separated and filtered. This precipitate was washed with 1094.94 g of methanol, and then dried under reduced pressure at 80° C. to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by the following (P-23). The chemical imidization rate was 95.3%. [Chemical 54]

<Synthesis Example 24> Synthesis of solvent-soluble polyimide (P-24) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries, Ltd. (stock)) 9.25g, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 18.15g, 4-methoxyphenol 0.06g, and N-ethyl-2 - 97.52 g of pyrrolidone was stirred at room temperature under air to dissolve, and 15.55 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-(4,4' 16.76 g of -isopropylidene (diphenoxy) diphthalic anhydride and 41.79 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 2 hours, and then stirred at 50° C. for 24 hours. The weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 30,055. 100.00 g of N-ethyl-2-pyrrolidone, 5.39 g of acetic anhydride, and 0.89 g of triethylamine were added to 50.00 g of the obtained polyamic acid, stirred at room temperature for 30 minutes in air, and then stirred at 60° C. for 3 hours. This solution was slowly added to 546.97 g of methanol under stirring, stirred for 10 minutes, and the obtained precipitate was separated and filtered. This precipitate was washed with 1093.94 g of methanol, and then dried under reduced pressure at 80° C. to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by the following (P-24). The chemical imidization rate was 95.3%. [Chemical 55]

<Comparative synthesis example 1> Synthesis of polyamic acid (P-25) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries system) 30.00g, 2,6-di-tert-butyl-p-cresol 0.13g, and N-ethyl-2-pyrrolidone 90.38g were stirred at room temperature under air to dissolve them, and pyromellitic anhydride 24.51 g and 37.11 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 13 hours, and then stirred at 80°C for 51 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-25), and had a weight average molecular weight (Mw) of 10,579 as measured in terms of polystyrene by GPC. [Chemical 56]

<Comparative synthesis example 2> Synthesis of polyamic acid (P-26) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries 42.28g of 4-methoxyphenol, 0.09g of 4-methoxyphenol, and 144.42g of N-ethyl-2-pyrrolidone were stirred at room temperature under air to dissolve them, and the 3,3',4,4'-linked 46.13 g of benzene tetracarboxylic dianhydride and 61.89 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 1 hour, and then stirred at 80° C. for 75 hours. A polyamic acid having a repeating unit structure represented by the following (P-26) was obtained. [Chemical 57]

<Comparative synthesis example 3> Synthesis of polyamic acid (P-27) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries ) 31.71g, 0.09g of 4-methoxyphenol, and 137.13g of N-ethyl-2-pyrrolidone were stirred at room temperature under air to dissolve them, and then 4,4'-(hexafluoroisopropylene 52.24 g of diphthalic anhydride and 58.77 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 3 hours, and then stirred at 80° C. for 75 hours. A polyamic acid having a repeating unit structure represented by the following (P-27) was obtained. [Chemical 58]

<Comparative Synthesis Example 4> Synthesis of polyamic acid (P-28) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries ) 18.00g, 0.08g of 2,6-di-tert-butyl-p-cresol, and 54.23g of N-ethyl-2-pyrrolidone were stirred at room temperature under air to dissolve them, and then 1,2, 13.22 g of 3,4-cyclobutanetetracarboxylic dianhydride and 30.40 g of N-ethyl-2-pyrrolidone were added to the system, stirred at room temperature for 62 hours, and then stirred at 40° C. for 34 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-28), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 42,930. [Chemical 59]

<Comparative Synthesis Example 5> Synthesis of polyamic acid (P-29) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries ) 15.00g, 0.06g of 2,6-di-tert-butyl-p-cresol, and 45.19g of N-ethyl-2-pyrrolidone were stirred at room temperature under air to dissolve them, and then 1,1' - 17.21 g of bicyclohexane-3,3',4,4'-tetracarboxylic acid-3,3',4,4'-dianhydride (BPDA-H, manufactured by Iwatani Gas Co., Ltd.), and N-acetate 30.12 g of 2-pyrrolidone was added to the system, stirred at room temperature for 62 hours, and then stirred at 40°C for 34 hours. The obtained polyamic acid had a repeating unit structure represented by the following (P-29), and the weight average molecular weight (Mw) measured in terms of polystyrene by GPC was 45,136. [Chemical 60]

<Comparative Synthesis Example 6>Synthesis of solvent-soluble polyimide (P-30) 2-(methacryloxy)ethyl 3,5-diaminobenzoate (BEM-S, Wako Pure Chemical Industries, Ltd. Industrial Co., Ltd.) 8.60g, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane 16.85g, 4-methoxyphenol 0.05g, and N-ethyl- 148.85 g of 2-pyrrolidone was stirred at room temperature under air to dissolve, and 27.72 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride and N-ethyl-2-pyrrolidone 63.79 g was added to the system, stirred at room temperature for 1 hour, and then stirred at 50°C for 87 hours. The weight average molecular weight (Mw) of the obtained polyamic acid measured in terms of polystyrene by GPC was 27,335. 60.00 g of N-ethyl-2-pyrrolidone, 4.49 g of acetic anhydride, and 0.58 g of pyridine were added to 60.00 g of the obtained polyamic acid, and stirred at room temperature for 30 minutes in air, and then stirred at 50° C. for 3 hours. This solution was slowly added to 437.76 g of methanol under stirring, stirred for 10 minutes, and the obtained precipitate was separated and filtered. This precipitate was washed with 875.52 g of methanol, and then dried under reduced pressure at 60° C. to obtain a solvent-soluble polyimide powder having a repeating unit structure represented by the following (P-30). The chemical imidization rate was 93.2%. [Chemical 61]

<Example 1> NK ester A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.42 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.17 g After mixing and dissolving, it filtered using the polypropylene filter of pore diameter 5 micrometers, and prepared the solution of the negative photosensitive resin composition.

<Example 2> 32.24 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.93 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.48 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.15 g, and KBM-5103 (3-acryloxy After dissolving 0.19 g of propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 3> 33.16 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-2) obtained in Synthesis Example 2, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.93 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.48g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethalone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.15g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 4> 22.08 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.10 g, KBM-5103 (3-acryloyloxy Propyltrimethoxysilane, 0.13 g of Shin-Etsu Chemical Co., Ltd., and 11.04 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 5> 32.49 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-3) obtained in Synthesis Example 3, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.97 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.49 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethalone-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.15g, KBM-5103( 3-Acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19g, and N-ethyl-2-pyrrolidone 0.71g were mixed and dissolved, and a polypropylene filter with a pore size of 5 μm was used Filter to prepare a solution of negative photosensitive resin composition.

<Example 6> 33.16 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-4) obtained in Synthesis Example 4, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.99 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.50 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethalone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.15g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.20 g was mixed, dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 7> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.80 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.45 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.13g, KBM-5103 (3-acryloyloxy Propyltrimethoxysilane, 0.18 g of Shin-Etsu Chemical Co., Ltd., and 2.48 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 8> 23.89 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-5) obtained in Synthesis Example 5, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.72 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.36g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.11g, KBM-5103( 3-Acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.14g, and N-ethyl-2-pyrrolidone 4.78g were mixed and dissolved, and a polypropylene filter with a pore size of 5 μm was used Filter to prepare a solution of negative photosensitive resin composition.

<Example 9> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.38 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.11 g, and KBM-5103 (3-acryloxy Propyltrimethoxysilane and Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 g were mixed and dissolved, and filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 10> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.38 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.11 g, and KBM-5103 (3-acryloxy After mixing and dissolving 0.15 g of propyltrimethoxysilane and Shin-Etsu Chemical Co., Ltd., it was filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 11> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.10 g, KBM-5103 (3-acryloyloxy Propyltrimethoxysilane, 0.13 g of Shin-Etsu Chemical Co., Ltd., and 11.04 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 12> 31.50 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-8) obtained in Synthesis Example 8, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.95 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.47g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trithiol-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.14g, KBM-5103( 3-Acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19g, and N-ethyl-2-pyrrolidone 1.75g were mixed and dissolved, and a filter made of polypropylene with a pore size of 5 μm was used Filter to prepare a solution of negative photosensitive resin composition.

<Example 13> 33.11 g of a solution (solid content concentration: 20% by weight) containing the polyamic acid (P-9) obtained in Synthesis Example 9, NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.32 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.33 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-tris(2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.10 g, and KBM-5103 (3-acryloxy After mixing and dissolving 0.13 g of propyltrimethoxysilane and Shin-Etsu Chemical Co., Ltd., it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 14> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.25 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.31 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.09g, KBM-5103 (3-acryloyloxy Propyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.12g, and N-ethyl-2-pyrrolidone 2.47 are dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive Solution of resin composition.

<Example 15> A solution (solid content concentration: 25% by weight) containing 23.66 g of the polyamic acid (P-11) obtained in Synthesis Example 11, 0.99 g of N-ethyl-2-pyrrolidone, and NK ESTER A- DOD-N (1,10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.59 g, IRGACURE [registered trademark] OXE01 (1,2-octane di Ketone, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.30 g, IRGANOX [registered trademark] 3114 (1,3, 5-ginseng(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri-2,4,6(1H,3H,5H)-trione, BASF JAPAN( Co., Ltd.) 0.09g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.12g were mixed and dissolved, and a polypropylene filter with a pore size of 5 μm was used Filter to prepare a solution of negative photosensitive resin composition.

<Example 16> 24.78 g of a solution (solid content concentration: 25% by weight) containing the polyamic acid (P-12) obtained in Synthesis Example 12, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.62 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.31g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimetha-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.09g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.12 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 17> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxy Propyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.17 g was mixed and dissolved, and filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 18> 28.42 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-13) obtained in Synthesis Example 13, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.85 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.43g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimetha-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.13g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.17 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 19> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.66 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.41 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.12 g, and KBM-5103 (3-acryloxy Propyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.17 g was mixed and dissolved, and filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 20> 28.42 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-14) obtained in Synthesis Example 14, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.85 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.43g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimetha-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.13g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.17 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 21> NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 1.28 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.32 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.10 g, KBM-5103 (3-acryloyloxy Propyltrimethoxysilane, 0.13 g of Shin-Etsu Chemical Co., Ltd., and 1.77 g of N-ethyl-2-pyrrolidone were mixed and dissolved, and filtered through a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 22> A solution (solid content concentration: 30% by weight) containing 37.81 g of the polyamic acid (P-16) obtained in Synthesis Example 16, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.27 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.57g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimetha-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.17g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.23g was mixed and dissolved, and filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 23> 65.34 g of a solution (solid content concentration: 25% by weight) containing polyamic acid (P-17) obtained in Synthesis Example 17, NK ESTER A-200 (polyethylene glycol diacrylate, new Nakamura Chemical Co., Ltd.) 3.27 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2 -(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.82 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-tert-butyl-4- Hydroxybenzyl)-1,3,5-trimethanone-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.25 g, and KBM-5103 (3-acryloxy Propyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.33 g was mixed and dissolved, and filtered using a polypropylene filter with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

<Example 24> 38.23 g of a solution (solid content concentration: 25% by weight) containing the polyamic acid (P-18) obtained in Synthesis Example 18, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.96 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.48g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethanium-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.14g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 25> 38.23 g of a solution (solid content concentration: 25% by weight) containing the polyamic acid (P-19) obtained in Synthesis Example 19, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.96 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.48g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethanium-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.14g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.19 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 26> A solution (solid content concentration: 20% by weight) containing 38.57 g of the polyamic acid (P-20) obtained in Synthesis Example 20, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.77 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethanium-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.12g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 27> 38.57 g of a solution (solid content concentration: 20% by weight) containing the polyamic acid (P-21) obtained in Synthesis Example 21, NK ESTER A-DOD-N (1,10-decane di Alcohol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 0.77 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio ) phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.39 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3,5-di-th Tributyl-4-hydroxybenzyl)-1,3,5-trimethanium-2,4,6(1H,3H,5H)-trione, BASF JAPAN Co., Ltd.) 0.12g, and KBM-5103 (3-Acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.15 g was mixed and dissolved, and then filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative photosensitive resin composition solution.

<Example 28> 11.02 g of powder of solvent-soluble polyimide (P-22) obtained in Synthesis Example 22, 25.71 g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N (1, 10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.20 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4 -(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.55 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3, 5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.17g , and KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.22 g were mixed, dissolved, and filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 29> 10.89 g of powder of solvent-soluble polyimide (P-23) obtained in Synthesis Example 23, 26.00 g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N (1, 10-Decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4 -(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.54 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3, 5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.16g , and KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.22 g were mixed, dissolved, and filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

<Example 30> 10.89 g of powder of solvent-soluble polyimide (P-24) obtained in Synthesis Example 24, 26.00 g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N (1, 10-Decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 2.18 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4 -(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.54 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3, 5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-trimethan-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.16g , and KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.22 g were mixed, dissolved, and filtered with a polypropylene filter with a pore size of 5 μm to prepare a negative type Solution of photosensitive resin composition.

＜Comparative example 1＞ 27.75 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-25) obtained in Comparative Synthesis Example 1, NK ESTER A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.42 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.17 After g mixing and dissolving, it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

＜Comparative example 2＞ 26.17 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-26) obtained in Comparative Synthesis Example 2, NK ESTER A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.57 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.39 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.16 After mixing and dissolving, filter through a polypropylene filter with a pore size of 5 μm to prepare a solution of a negative photosensitive resin composition.

＜Comparative example 3＞ 25.08 g of a solution (solid content concentration: 30% by weight) containing the polyamic acid (P-27) obtained in Comparative Synthesis Example 3, NK ESTER A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.50 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.38 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.15 After g mixing and dissolving, it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

＜Comparative example 4＞ 27.96 g of a solution (solid content concentration: 27% by weight) containing the polyamic acid (P-28) obtained in Comparative Synthesis Example 4, NK ESTER A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.51 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.38 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.15 After g mixing and dissolving, it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

＜Comparative example 5＞ NK ESTER A-200 (polyethylene glycol diacrylate, Shin-Nakamura Chemical Co., Ltd.) 1.67 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.42 g, and KBM-5103 (3-acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.17 After g mixing and dissolving, it was filtered using a filter made of polypropylene with a pore diameter of 5 μm to prepare a solution of a negative photosensitive resin composition.

＜Comparative example 6＞ 9.14 g of powder of solvent-soluble polyimide (P-30) obtained in Comparative Synthesis Example 6, 16.98 g of N-ethyl-2-pyrrolidone, and NK ESTER A-DOD-N (1 , 10-decanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 1.83 g, IRGACURE [registered trademark] OXE01 (1,2-octanedione, 1-[ 4-(phenylthio)phenyl-, 2-(O-benzoyl oxime)], BASF JAPAN Co., Ltd.) 0.46 g, IRGANOX [registered trademark] 3114 (1,3,5-ginseng (3 ,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, manufactured by BASF JAPAN Co., Ltd.) 0.14 g, and 0.18 g of KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, dissolved, and filtered using a polypropylene filter with a pore size of 5 μm to prepare a negative A solution of photosensitive resin composition.

[Photosensitivity evaluation] Negative-type photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 using a spin coater (CLEAN TRACK ACT-8, manufactured by Tokyo Power Technology Co., Ltd.) Coat it on an 8-inch silicon wafer and calcinate it at 115°C for 180 seconds or 270 seconds to form a photosensitive resin film with a film thickness of 5 to 15 μm on the wafer. Then, exposure was performed using an i-ray stepper (NSR-2205i12D, manufactured by Nikon Co., Ltd.). Furthermore, using an automatic developing device (AD-1200, manufactured by MIKASA Co., Ltd.), cyclopentanone was used as a developing solution, and after spraying and developing for 20 to 240 seconds, propylene glycol monomethyl ether acetate (PGMEA) was used as a rinse. liquid, spray and rinse for 10 seconds. Use an interference film thickness meter (Lambda ACE VM-2110, manufactured by SCREEN Co., Ltd.) to measure the film thickness immediately after film formation and the film thickness after development of 0mJ/cm ² (unexposed area) and 300mJ/cm ² (exposed area) , compare the film thickness of the unexposed part and the exposed part. Table 1 shows the measurement results of the film thickness.

[Table 1]

From the results in Table 1, for the negative photosensitive resin compositions of Examples 1 to 30, the photosensitive resin film in the unexposed area (0mJ/cm ² ) was fully dissolved (developed) after development, and the exposed area (300mJ/cm 2 ) was fully dissolved (developed). ² ) The photosensitive resin film remains without being dissolved (developed). That is, a clear difference in dissolution (dissolution contrast) of the photosensitive resin film is obtained between the exposed part and the unexposed part, so it is ideally suitable for the production of relief patterns that are developed using a general-purpose organic solvent such as cyclopentanone Negative photosensitive resin composition for processing. On the other hand, in the photosensitive resin compositions of Comparative Example 1, Comparative Example 2, Comparative Example 4, and Comparative Example 5, the photosensitive resin film in the unexposed area (0mJ/cm ² ) was not fully dissolved (developed) after development and remained . That is, the exposed part and the unexposed part do not have a clear dissolution contrast, and it is not suitable as a negative-type photosensitive resin composition for developing a relief pattern using a general-purpose organic solvent such as cyclopentanone.

[Evaluation of electrical properties] Spin-coat the negative-type photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 on a 4-inch silicon wafer coated with an aluminum foil with a thickness of 20 μm, and use a hot plate Calcined at 115°C for 180 seconds or 270 seconds to form a photosensitive resin film on the aluminum foil. Then use an i-ray aligner (PLA-501, manufactured by Canon Co., Ltd.), after fully exposing the wafer at 500mJ/cm ² , calcine at 160°C for 1 hour in a nitrogen atmosphere, followed by calcination at 230°C Calcination was performed for 1 hour. Furthermore, the calcined aluminum foil was immersed in 6N hydrochloric acid to dissolve the aluminum foil to obtain a thin film. Then the obtained film was dried under reduced pressure at 80°C for 2 hours, and after being placed in an environment with a temperature of about 25°C and a humidity of about 42% for 24 hours, a cavity resonator (TMR-1A, KEYCOM (Stock) system) to measure the dielectric tangent. The measurement conditions of the dielectric tangent are as follows.・Measurement method: Disturbance cavity resonator method ・Vector network analyzer: FieldFox N9926A (manufactured by KEYSIGHT TECHNOLOGIES Co., Ltd.) ・Cavity resonator: TMR-1A (manufactured by KEYCOM Co., Ltd.) ・Cavity volume: 1192822mm ³・Measurement frequency: about 1GHz ・Sampling tube: made of PTFE, inner diameter: 3mm, length about 30mm (manufactured by KEYCOM Co., Ltd.)

[Evaluation of Mechanical Properties] Spin-coat the negative photosensitive resin compositions prepared in Examples 1 to 30 and Comparative Examples 1 to 6 on an aluminum wafer with a thickness of 100 nm, and perform 180 °C on a hot plate at 115 ° C. seconds or 270 seconds to form a photosensitive resin film on an aluminum wafer. Then use an i-ray aligner (PLA-501, manufactured by Canon Co., Ltd.), after fully exposing the wafer under the condition of 500mJ/cm ² , perform calcination at 160°C for 1 hour in a nitrogen environment, followed by calcination at 230 °C for 1 hour calcination. Furthermore, after dicing the photosensitive resin film with a dicing saw (DAD323, manufactured by DISCO Co., Ltd.) at intervals of 5 mm in width, the aluminum wafer was immersed in 6N hydrochloric acid to dissolve aluminum to obtain a film with a width of 5 mm. Then, the tensile elongation of the film was measured for the obtained film using a desktop precision universal testing machine (autograph AGS-10kNX, manufactured by Shimadzu Corporation). The measurement conditions of the tensile elongation are as follows.・Desktop precision universal testing machine: Autograph AGS-10kNX (manufactured by Shimadzu Corporation) ・Film width: 5mm ・Distance between grippers: 25mm Here, the tensile elongation is 50 %, means that the film is extended until 1.5 times, in other words, it means that the film breaks when the distance between the grippers is 1.5 times (37.5mm).

Table 2 shows the measurement results of dielectric tangent and tensile elongation.

[Table 2]

From the results in Table 2, the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 have lower dielectric tangent values at 1 GHz than those of Comparative Examples 1 to 5. Also, the films obtained from the negative photosensitive resin compositions of Examples 1 to 30 had higher values of tensile elongation than those of Comparative Examples 1 to 6. That is to say, the negative photosensitive resin compositions of Examples 1 to 30 can be used to make undulating patterns, and at the same time have the advantages of low dielectric tangent and high tensile elongation, and are suitable for use in electronics that require excellent electrical and mechanical properties. Manufacturing of materials.

Claims (18)

A photosensitive resin composition, comprising: a reaction product of an aromatic diamine compound having a photopolymerizable group and a tetracarboxylic acid derivative having three or more aromatic rings, and a solvent. The photosensitive resin composition according to Claim 1, wherein the reaction product is polyamic acid or polyimide obtained by dehydrating and ring-closing polyamic acid. The photosensitive resin composition as claimed in claim 2, wherein the polyamide acid has at least a structural unit represented by the following formula (1), and the polyimide has at least a structural unit represented by the following formula (2),

In formula (1), Ar ₁ represents a divalent organic group having a photopolymerizable group and an aromatic ring, Ar ₂ represents a tetravalent organic group having 3 or more aromatic rings,

In formula (2), Ar ₃ represents a divalent organic group having a photopolymerizable group and an aromatic ring, and Ar ₄ represents a tetravalent organic group having three or more aromatic rings. As the photosensitive resin composition of claim item 3, wherein, Ar in the formula (1) and Ar in the formula ( ₂ ) are _four -valent organic groups represented by the following formula (3),

In formula (3), X ₁ and X ₂ each independently represent a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond or a sulfonyl bond; R ₁ and R ₂ each independently represent an alkyl group with 1 to 6 carbon atoms that may also be substituted; Y represents a divalent organic group represented by the following formula (3-1) or (3-2); n1 and n2 represent independently An integer from 0 to 3; when there are multiple R _1s , the multiple R _1s can be the same or different; when there are multiple R _2s , the multiple R _2s can be the same or different; * represents an atomic bond;

In formula (3-1), Z ₁ represents a direct bond, an ether bond, an ester bond, an amide bond, a carbamate bond, a urea bond, a thioether bond, or a sulfonyl bond; R ₃ and R ₄ are each Independently represent a hydrocarbon group with a carbon number of 1 to 6 that may also be substituted; m1 represents an integer of 0 to 3; n3 and n4 each independently represent an integer of 0 to 4; when there are multiple Z ₁ , multiple Z ₁ can be _The same or different; when there are multiple _n4s , multiple _n4s can be the same or different; when there are multiple R3s, multiple R3s can be the same or different; when there are multiple R4s, multiple _R4s can be the same It can also be different; * represents an atomic bond; in formula (3-2), Z ₂ represents a divalent organic group represented by the following formula (4) or (5); R ₅ and R ₆ represent independently and can also be substituted A hydrocarbon group with 1 to 6 carbon atoms; n5 and n6 each independently represent an integer from 0 to 4; when there are multiple R5s, multiple _R5s may be the same or different _; when there are multiple _R6s , multiple _R6s Can be the same or different; * means atomic bond;

In formula (4), R ₇ and R ₈ each independently represent a hydrogen atom, or a hydrocarbon group with 1 to 6 carbon atoms that may also be substituted by a halogen atom; * represents an atomic bond; in formula (5), R ₉ and R ₁₀ each independently represent an alkylene group having 1 to 6 carbon atoms which may also be substituted or an arylylene group having 6 to 10 carbon atoms which may also be substituted; * represents an atomic bond. As the photosensitive resin composition of claim item 3, wherein, Ar in the formula ( ₁ ) and Ar in the formula ( ₂ ) are divalent organic groups represented by the following formula (6),

In formula (6), Z ₃ represents ether bond, ester bond, amide bond, urethane bond or urea bond, Z ₄ represents direct bond, ester bond or amide bond; Z ₅ represents direct bond, ether bond, ester bond, amide bond, urethane bond, urea bond, thioether bond, or sulfonyl bond; m2 represents an integer from 0 to ₁ ; R11 represents a direct bond, or it can also be substituted by a hydroxyl group An alkylene group having 2 to 6 carbon atoms, R ₁₂ represents a hydrogen atom or a methyl group; * represents an atomic bond. The photosensitive resin composition as claimed in item 5, wherein Z ₃ and Z ₄ in the formula (6) are ester bonds. The photosensitive resin composition as claimed in item 5, wherein R ₁₁ in the formula (6) is 1,2-ethylene. The photosensitive resin composition of claim 1 further contains a photoradical polymerization initiator. The photosensitive resin composition as claimed in claim 1 further contains a cross-linking compound. For example, the photosensitive resin composition of claim 1 is used for forming an insulating film. The photosensitive resin composition of claim 1 is a negative photosensitive resin composition. A resin film is a calcined product of the coating film of the photosensitive resin composition according to any one of claims 1 to 11. The resin film as in Claim 12 is an insulating film. A photoresist film comprising: a substrate film; a photosensitive resin layer formed of the photosensitive resin composition according to any one of Claims 1 to 11; and a surface coating film. A method of manufacturing a substrate with a hardened relief pattern, comprising the following steps: (1) Coating the photosensitive resin composition according to any one of Claims 1 to 11 on a substrate to form a photosensitive resin layer on the substrate; (2) exposing the photosensitive resin layer; (3) developing the exposed photosensitive resin layer to form a relief pattern; (4) The relief pattern is heat-treated to form a hardened relief pattern. The method of manufacturing a substrate with a hardened relief pattern according to claim 15, wherein the developer used in the development is an organic solvent. A substrate with a hardened relief pattern is produced by using the method for manufacturing a substrate with a hardened relief pattern according to claim 15 or 16. A semiconductor device comprising a semiconductor element and a cured film provided on or under the semiconductor element, The cured film is a cured relief pattern formed of the photosensitive resin composition according to any one of Claims 1 to 11.