阅读说明：本技术 聚合物、光敏树脂组合物、图案形成方法、光敏干膜以及电气及电子部件保护用覆膜 (Polymer, photosensitive resin composition, pattern forming method, photosensitive dry film, and coating film for protecting electric and electronic parts ) 是由 竹村胜也 饭尾匡史 浦野宏之 本田和也 于 2019-08-01 设计创作，主要内容包括：本发明的目的在于提供一种聚合物,其易溶于广泛使用且安全的有机溶剂,可溶于碱性水溶液,且能够作为可形成精细图案并能够得到高分辨率的正型光敏树脂组合物的基础树脂而使用。所述聚合物具有聚酰胺、聚酰胺酰亚胺或聚酰亚胺结构单元,其特征在于,所述聚合物选自聚酰胺、聚酰胺酰亚胺、聚酰亚胺、聚酰亚胺前体、聚苯并噁唑、聚苯并噁唑前体,所述聚合物包含二胺与下述通式(3)所表示的四羧酸二酐及下述通式(4)所表示的二羧酸或二羧酸卤化物中的任意一种以上的反应生成物,所述二胺含有下述通式(1)所表示的二胺及通式(2)所表示的二胺中的任意一种以上。[化学式1]<Image he="243" wi="700" file="DDA0002152940050000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式2]<Image he="232" wi="700" file="DDA0002152940050000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式3]<Image he="323" wi="700" file="DDA0002152940050000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式4]<Image he="273" wi="700" file="DDA0002152940050000021.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。(The purpose of the present invention is to provide a polymer which is easily soluble in a widely used and safe organic solvent, is soluble in an alkaline aqueous solution, and can be used as a base resin capable of forming a fine pattern and obtaining a positive photosensitive resin composition with high resolution. The polymer has polyamide, polyamide-imide or polyimide structural units, and is characterized in that the polymer is selected from polyamide, polyamide-imide or polyimide structural unitsThe polyimide polymer is a polymer comprising a reaction product of a diamine containing at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2), a tetracarboxylic dianhydride represented by the following general formula (3), and a dicarboxylic acid or a dicarboxylic acid halide represented by the following general formula (4). [ chemical formula 1] [ chemical formula 2] [ chemical formula 3] [ chemical formula 4] 。)

1. A polymer having a polyamide, polyamideimide or polyimide structural unit, characterized in that the polymer is selected from the group consisting of polyamides, polyamideimides, polyimides, polyimide precursors, polybenzoxazoles and polybenzoxazole precursors, and the polymer comprises a reaction product of a diamine containing at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2) with a tetracarboxylic dianhydride represented by the following general formula (3) and at least one of a dicarboxylic acid or a dicarboxylic acid halide represented by the following general formula (4),

in the formula (I), the compound is shown in the specification,z represents an alicyclic structure to which an alicyclic or aromatic ring having 3 to 20 carbon atoms is bonded or an alicyclic structure to which an alicyclic or aromatic ring containing or interposed between hetero atoms is bonded, A represents a hydroxyl group or a halogen atom, j represents 0 or 1, and when j is 0, it represents that the phthalic anhydride structure in the general formula (3) is directly bonded to the cyclic structure Z, the benzoic acid structure in the general formula (4) is directly bonded to the cyclic structure Z, and when j is 1, X is₁、X₂Represents a divalent linking group.

2. The polymer according to claim 1, wherein the alicyclic structure Z of the general formulae (3) and (4) is represented by the following general formula (11) or (12),

wherein the dotted line represents a bond, and k represents an integer of 0 or 1 or more; y is₂Represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16); when k is 1, Y₁Represents a divalent group selected from any one of the following general formulae (17), (18), (19), and (20); when k is 2 or more, Y₁Represents the following general formula (17); r¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Are bonded to each other to form an alicyclic or aromatic ring,

wherein the dotted line represents a bond, R⁷Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms,

wherein the dotted line represents a bond, R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Bonded to each other to form an alicyclic structure or an aromatic ring structure; m and p represent 0 or an integer of 1 to 9; n represents 0 or 1; y is₃Represents a divalent group selected from any one of the general formulae (13), (14), (15), (16), (17), (18), (19), and (20).

3. The polymer according to claim 1, wherein the divalent linking group X of the general formulae (3) and (4)₁、X₂Is a group represented by any one of the following general formulae (5), (6), (7), (8), (9) and (10),

in the formula, the dotted line represents a bond.

4. The polymer according to claim 2, wherein the divalent linking group X of the general formulae (3) and (4)₁、X₂Is a group represented by any one of the following general formulae (5), (6), (7), (8), (9) and (10),

in the formula, the dotted line represents a bond.

5. The polymer according to claim 1, wherein the diamine represented by the general formula (1) is represented by the following general formula (21),

6. the polymer according to claim 1, wherein the reaction product further contains a unit of a tetracarboxylic acid diester represented by the following general formula (22),

wherein W1 is a tetravalent organic group, R¹⁶Is represented by the following general formula (23),

wherein the dotted line represents a bond, V₁Is an (r +1) -valent organic group, Rf is an aromatic group which may be substituted by a linear, branched or cyclic alkyl group or alkyl group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms are substituted by fluorine atoms, r represents 1,2 or 3, and q represents 0 or 1.

7. The polymer of claim 6, wherein R in the general formula (22)¹⁶Is an organic group selected from any one of the groups represented by the following general formulae (24), (25), (26) and (27),

wherein the dotted line represents a bond; rf is the same as the above, Ra and Rb are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, V₂And V₃Is a linear or branched alkylene group having 1 to 6 carbon atoms, q1 represents an integer of 0 to 6, q2 represents an integer of 1 to 6, q3 represents an integer of 0 to 6, q4 represents 1 to E6, q5 represents an integer of 0 to 6, q6 represents 0 or 1, and q7 represents 0 or 1.

8. The polymer of claim 6, wherein R in the general formula (22)¹⁶Is a group represented by the following general formula (23-1),

*--------CH₂-CH₂-Rf (23-1)

wherein the dotted line represents a bond; rf is the same as said Rf.

9. The polymer according to claim 1, wherein the alicyclic structure Z of the general formula (3) is a tetracarboxylic dianhydride selected from any one of the following general formulae (Z-1) and (Z-2), and the alicyclic structure Z of the general formula (4) is any one or more selected from dicarboxylic acids or dicarboxylic acid halides selected from any one of the following formulae (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) and (Z-8),

wherein the dotted line represents a bond, R¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Bonded to each other to be an alicyclic or aromatic ring; r⁷Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms; r⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Respectively bonded to form an alicyclic structure or an aromatic ring structure.

10. A positive photosensitive resin composition, characterized by comprising:

(A) a polymer as claimed in any one of claims 1 to 9;

(B) a photosensitizer generating an acid by light, which is a compound having a quinonediazide structure;

(D) a solvent.

11. The positive photosensitive resin composition according to claim 10, further comprising the following component (C),

(C) a crosslinking agent which is one or more selected from the group consisting of an amino condensate obtained by modifying formaldehyde or formaldehyde-alcohol, 1 phenol compound having an average of 2 or more methylol groups or alkoxymethyl groups in the molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (C-2),

wherein the dotted line represents a bond, Rc represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

12. The positive photosensitive resin composition according to claim 10, further comprising (E) a compound that generates an acid or a radical by heat.

13. A pattern forming method is characterized by comprising the following steps:

(1) a step of applying the positive photosensitive resin composition according to claim 10 onto a substrate to form a photosensitive material coating film;

(2) then, after the heating treatment, exposing the photosensitive material coating film with a high-energy ray or electron beam having a wavelength of 190-500 nm through a photomask;

(3) and a step of developing the substrate with a developer of an alkaline aqueous solution.

14. The pattern forming method according to claim 13, further comprising: (4) and post-curing the coating film patterned by the development at a temperature of 100 to 300 ℃.

15. A photosensitive dry film having a structure in which a photosensitive resin layer having a film thickness of 5 to 100 μm is sandwiched between a support film and a protective film, wherein the composition for forming the photosensitive resin layer is the positive photosensitive resin composition according to claim 10.

16. A method for manufacturing a photosensitive dry film, comprising the steps of:

(i) a step of forming a photosensitive resin layer by continuously applying the positive photosensitive resin composition according to claim 10 on a support film;

(ii) a step of continuously drying the photosensitive resin layer;

(iii) and further laminating a protective film on the photosensitive resin layer.

17. A pattern forming method is characterized by comprising the following steps:

(i) a step of closely bonding the photosensitive resin layer exposed by peeling the protective film from the photosensitive dry film according to claim 15 to the substrate;

(ii) exposing the photosensitive resin layer with a high-energy ray or an electron beam having a wavelength of 190 to 500nm through the support film or through a photomask in a state where the support film is peeled;

(iii) and a step of developing with a developer.

18. The pattern forming method according to claim 17, characterized by further comprising: (iv) and post-curing the coating film patterned by the development at a temperature of 100 to 300 ℃.

19. A coating film for protecting electrical and electronic parts, which is formed from a cured coating film obtained by curing the positive photosensitive resin composition according to claim 10.

Technical Field

The present invention relates to a polymer containing a polyamide, a polyamideimide, or a polyimide structure, a photosensitive resin composition, a pattern forming method using the composition, a photosensitive dry film, and a film for protecting electric and electronic parts.

Background

With the miniaturization and high performance of various electronic devices such as personal computers, digital cameras, and cellular phones, demands for further miniaturization, thinning, and high density of semiconductor elements have been rapidly increasing. Therefore, it is desired to develop a photosensitive insulating material that can cope with an increase in substrate area when improving productivity, and that is fine and has a high aspect ratio (aspect ratio) on a substrate in a high-density mounting technology such as chip size packaging, Chip Scale Packaging (CSP), or three-dimensional lamination.

In a high-density mounting technique such as three-dimensional lamination, a polyimide film has been used as a protective film or an insulating layer as a photosensitive insulating material which can be patterned on a substrate, and insulation properties, mechanical strength, adhesion to a substrate, and the like have been attracting attention.

Conventionally, as photosensitive polyimide-based materials, materials using polyamic acid as a polyimide precursor, for example, materials obtained by introducing a photosensitive group into a carboxyl group of polyamic acid through an ester bond have been proposed (patent documents 1 and 2). However, in these proposals, in order to obtain a target polyimide coating film after forming a patterned coating film, it is necessary to perform imidization treatment at a high temperature exceeding 300 ℃.

As a method for improving this problem, a photosensitive polyimide using an imidized solvent-soluble resin for the purpose of lowering the curing temperature later has been proposed (patent documents 3 and 4). The negative photosensitive resin composition using polyimide described in patent document 3 is developed using N-methyl-2-pyrrolidone (NMP) in pattern formation. However, N-methyl-2-pyrrolidone presents a burden on the environment or health concerns that can be detrimental, particularly with attractive respirators. N-methyl-2-pyrrolidone is included in SVHC (substances of high interest), particularly in the REACH (Registration, Evaluation, Automation and recovery of Chemicals) regulations in Europe. Therefore, N-methyl-2-pyrrolidone is a solvent that is desired to be avoided as much as possible in pattern formation. In addition, in patent document 3, resolution performance in pattern formation is not specifically described.

Patent document 4 discloses a method for forming a pattern of a photosensitive resin composition, in which a material using a polyamic acid as a polyimide precursor, for example, a resin obtained by introducing an ester bond into a carboxyl group of a polyamic acid is used, and it is further disclosed that heating for obtaining a desired polyimide film can be performed at a relatively low temperature of 250 ℃. However, the solvent of the photosensitive resin composition is N-methyl-2-pyrrolidone, and the developing process uses an organic solvent of N-methyl-2-pyrrolidone. According to the above description, the use of an organic solvent of N-methyl-2-pyrrolidone in the developer is avoided as much as possible. In this patent document, a specific resolution is not disclosed.

Further, patent document 5 relates to pattern formation of a negative-type photosensitive resin composition using a precursor of polyimide. Although the solvent of the photosensitive resin composition is N-methyl-2-pyrrolidone, cyclopentanone is used for developing the photosensitive resin composition. Resolution performance has been specifically disclosed, enabling aspect ratios above 1. However, the aspect ratio is not a ratio of the film thickness or the pattern height to the pattern size of the final product, but represents a ratio of the film thickness to the size after coating and drying, and the resolution performance is not a practical value and needs to be improved. In addition, when a widely used organic solvent such as cyclopentanone is used, there is occasionally a disadvantage that the pattern shape immediately after development is likely to become an overhanging profile due to swelling of the film during development.

On the other hand, the photosensitive resin composition proposed in patent document 6 uses an imidized base resin (base resin) constructed in view of low-temperature curing. Since the solvent of the composition is cyclopentanone and an alkaline aqueous solution is also used in the developing step, the use of N-methyl-2-pyrrolidone can be avoided. But resolution performance still needs to be improved. That is, the pattern formation using the photosensitive resin composition described in patent document 6 is performed in an extremely thin film, and the size of the pattern to be analyzed is also large. This lack of resolution performance is considered to be caused by the lack of solubility of the polyimide resin disclosed as the base resin in an alkaline aqueous solution for a developer in patent document 6.

In recent years, as resolution performance of a photosensitive insulating material in a high-density mounting technique such as three-dimensional lamination, an aspect ratio of a pattern to be formed (a film thickness of a finished product (or a height of the pattern)/a size of the pattern) is required to be about 1 or more and about 2. That is, when the required film thickness or pattern height of the final product is 10 μm, it is necessary to form a pattern having a size of 10 μm or less or a pattern of approximately 5 μm.

Further, patent document 7 relates to pattern formation of a negative-type photosensitive resin composition using a polyimide precursor. The solvent of the photosensitive resin composition is gamma-butyrolactone, and the developing solution is an alkaline aqueous solution. In this pattern forming method, the resin of the polyimide precursor contains an alkali-soluble group such as an acid group, i.e., a carboxyl group, thereby improving the solubility in an alkaline aqueous solution of a developer, and pattern formation by development with an alkaline aqueous solution is performed. Development based on an alkaline aqueous solution has advantages of being less likely to cause swelling, good pattern shape, and improved resolution performance. However, when the resin contains such an alkali-soluble group, the following problems cannot be solved although the resin advantageously acts to improve resolution: after curing, the resist composition is less resistant to a highly alkaline stripping solution used in a step of applying metal wiring for stripping a resist pattern for plating. In order to form an excellent protective insulating film, it is necessary to completely block the alkali-soluble group present on the resin or completely remove it from the system.

Further, patent document 8 relates to pattern formation of a negative-type photosensitive resin composition using a polyimide precursor. The solvent of the photosensitive resin composition is also N-methyl-2-pyrrolidone, and must be improved. Further, since this photosensitive resin composition uses a polyimide precursor as a base resin, it is necessary to imidize the polyimide precursor by heat treatment after patterning, and heat treatment at 350 ℃ is exemplified, but in consideration of heating conditions allowed for an apparatus for mounting, it is obvious that a heating temperature of high-density mounting technology such as three-dimensional lamination, which has been required in recent years, is desired to be 200 ℃ or lower, and thus it departs from the actual requirements. Further, since the base resin of the photosensitive resin composition is a precursor of polyimide, a detachment reaction of an ester portion occurs during the imidization reaction during the heat treatment, and thus the shrinkage of the film is large. With the increase in density, even in the case of a photosensitive resin composition having improved resolution performance, if the film shrinkage after curing by heat treatment is large, the aspect ratio of the final pattern cannot be obtained, which is not preferable.

Therefore, in the future, with the increase in density and integration of chips, pattern miniaturization is also progressing in the rewiring technology of insulating protective films, and therefore, in photosensitive resin compositions using polymers having polyimide or polyimide precursor structural units, there is a strong demand for compositions that can achieve high resolution without impairing excellent characteristics such as mechanical strength and adhesion of polyimide patterns and protective coatings obtained by heating.

In addition, it is strongly required that the insulating protective film subjected to pattern formation and curing has heat resistance in various steps and resistance to various chemicals used.

Disclosure of Invention

Technical problem to be solved by the invention

The present invention has been made to solve the above problems, and an object of the present invention is to provide a polymer which is easily soluble in a widely used and safe organic solvent, is soluble in an aqueous alkaline solution, and can be used as a base resin for a positive photosensitive resin composition capable of forming a fine pattern and obtaining a high resolution, the polymer being selected from the group consisting of polyamide, polyamideimide, polyimide, a polyimide precursor, polybenzoxazole and a polybenzoxazole precursor. Another object of the present invention is to provide a positive photosensitive resin composition which can be cured at a low temperature of 200 ℃ or less, and which can impart a high glass transition temperature (Tg) excellent in mechanical strength and heat resistance to a film cured after pattern formation, using a resin containing the polymer which is soluble in an alkaline aqueous solution, has excellent resolution, and can form a fine pattern, in pattern formation.

Means for solving the problems

In order to achieve the above object, the present invention provides a polymer having a polyamide, polyamideimide or polyimide structural unit, wherein the polymer is selected from the group consisting of a polyamide, polyamideimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, the polymer comprising a reaction product of a diamine comprising at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2) and a tetracarboxylic dianhydride represented by the following general formula (3) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (4).

[ chemical formula 1]

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

Wherein Z represents an alicyclic structure to which an alicyclic or aromatic ring having 3 to 20 carbon atoms is bonded or an alicyclic structure to which an alicyclic or aromatic ring containing or interposed by a hetero atom is bonded, A represents a hydroxyl group or a halogen atom, j represents 0 or 1, and when j is 0, it represents that the phthalic anhydride structure in the general formula (3) is directly bonded to the cyclic structure Z, the benzoic acid structure in the general formula (4) is directly bonded to the cyclic structure Z, and when j is 1, X is₁、X₂Represents a divalent linking group.

The polymer of the present invention is easily soluble in a widely used and safe organic solvent, is soluble in an aqueous alkali solution, and can be used as a base resin for forming a fine pattern and obtaining a positive photosensitive resin composition with high resolution.

In this case, the alicyclic structure Z of the general formulae (3) and (4) is preferably the following general formula (11) or (12).

[ chemical formula 5]

Wherein the dotted line represents a bond, and k represents an integer of 0 or 1 or more; y is₂Represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16); when k is 1, Y₁Represents a divalent group selected from any one of the following general formulae (17), (18), (19), and (20); when k is 2 or more, Y₁Represents the following general formula (17); r¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Bonded to each other to form an alicyclic or aromatic ring.

[ chemical formula 6]

Wherein the dotted line represents a bond, R⁷Represents a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms.

[ chemical formula 7]

Wherein the dotted line represents a bond, R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Represent the same or different substituents and represent a hydrogen atomA linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, a methyl group, an ethyl group, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Bonded to each other to form an alicyclic structure or an aromatic ring structure; m and p represent 0 or an integer of 1 to 9; n represents 0 or 1; y is₃Represents a divalent group selected from the group consisting of the above general formulae (13), (14), (15), (16), (17), (18), (19) and (20).

Such a polymer is more soluble in a widely used and safe organic solvent, is soluble in an aqueous alkaline solution, and can be used as a base resin for a positive photosensitive resin composition capable of forming a fine pattern and obtaining a high resolution.

Furthermore, the divalent linking groups X of the general formulae (3) and (4) of the polymers of the invention are preferred₁、X₂Is a group represented by any one of the following general formulae (5), (6), (7), (8), (9) and (10).

[ chemical formula 8]

In the formula, the dotted line represents a bond.

Such a polymer is further easily soluble in an organic solvent which is widely used as a solvent for a photosensitive resin composition and is safe, and is useful as a base resin for a photosensitive resin composition, and a film which is cured after pattern formation using the photosensitive resin composition is excellent in mechanical strength and heat resistance.

In addition, the diamine represented by the general formula (1) in the polymer of the present invention is preferably represented by the following general formula (21).

[ chemical formula 9]

In the case of such a polymer, by using a photosensitive resin composition containing the polymer, a developer of an alkaline aqueous solution can be used more suitably in the pattern formation and the development step, and the dissolution rate of the base resin in the developer of an alkaline aqueous solution can be easily measured and controlled, so that the resolution of the photosensitive resin composition can be further improved.

The polymer of the present invention may further contain a unit of a tetracarboxylic acid diester represented by the following general formula (22) in the reaction product.

[ chemical formula 10]

Wherein W1 is a tetravalent organic group, R¹⁶Is represented by the following general formula (23).

[ chemical formula 11]

Wherein the dotted line represents a bond, V₁Is an (r +1) -valent organic group, Rf is an aromatic group which may be substituted by a linear, branched or cyclic alkyl group or alkyl group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms are substituted by fluorine atoms, r represents 1,2 or 3, and q represents 0 or 1.

Such a polymer is further easily soluble in a widely used and safe organic solvent.

In this case, R in the general formula (22) of the polymer of the present invention is preferably R¹⁶Is an organic group selected from any one of the groups represented by the following general formulae (24), (25), (26) and (27).

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

Wherein the dotted line represents a bond; rf is the same as above, Ra and Rb are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, V₂And V₃Is a linear or branched alkylene group having 1 to 6 carbon atoms, q1 represents an integer of 0 to 6, q2 represents an integer of 1 to 6, q3 represents an integer of 0 to 6, q4 represents an integer of 1 to 6, q5 represents an integer of 0 to 6, q6 represents 0 or 1, and q7 represents 0 or 1.

Further, R in the general formula (22) of the polymer of the present invention is preferably R¹⁶Is a group represented by the following general formula (23-1).

[ chemical formula 16]

＊--------CH₂-CH₂-Rf (23-1)

Wherein the dotted line represents a bond; rf is the same as described above.

Such a polymer is more soluble in a widely used and safe organic solvent.

Further, it is preferable that the alicyclic structure Z of the general formula (3) of the polymer of the present invention is a tetracarboxylic dianhydride selected from any one of the following general formulae (Z-1) and (Z-2), and the alicyclic structure Z of the general formula (4) is any one or more selected from dicarboxylic acids or dicarboxylic acid halides selected from any one of the following formulae (Z-3), (Z-4), (Z-5), (Z-6), (Z-7) and (Z-8).

[ chemical formula 17]

[ chemical formula 18]

[ chemical formula 19]

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

Wherein the dotted line represents a bond, R¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Bonded to each other to be an alicyclic or aromatic ring; r⁷Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms; r⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Represent the same or different substituents, and represent a hydrogen atom, a methyl group, an ethyl group, a C3-12 linearA linear, branched, cyclic alkyl group, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Respectively bonded to form an alicyclic structure or an aromatic ring structure.

Such a polymer is preferable because the corresponding tetracarboxylic dianhydride or dicarboxylic acid can be easily obtained or synthesized. Further, the alicyclic structure Z of (4) is selected from any dicarboxylic acids of the above-mentioned formulae (Z-3) to (Z-8), and is similarly easily available or can be synthesized. Further, the dicarboxylic acid halide can be easily obtained by reacting these dicarboxylic acids with a halogenating agent.

Further, the present invention provides a positive photosensitive resin composition comprising: (A) the above-mentioned polymer; (B) a photosensitizer which generates an acid by light, which is a compound having a quinonediazide structure; (D) a solvent.

The positive photosensitive resin composition of the present invention can form a fine pattern having excellent resolution and being soluble in an alkaline aqueous solution during pattern formation, can be cured at a low temperature of 200 ℃ or less, and can impart a high glass transition temperature, which is excellent in mechanical strength and heat resistance, to a film cured after pattern formation.

The positive photosensitive resin composition of the present invention may further contain the following component (C).

(C) And a crosslinking agent which is one or two or more selected from the group consisting of an amino condensate obtained by modifying formaldehyde or formaldehyde-alcohol, a phenol compound having an average of 2 or more methylol groups or alkoxymethyl groups in 1 molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).

[ chemical formula 25]

Wherein the dotted line represents a bond, Rc represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

Such a positive photosensitive resin composition is more excellent in resolution in pattern formation, and the cured film after pattern formation is more excellent in mechanical strength and heat resistance.

In addition, the positive photosensitive resin composition of the present invention preferably further contains (E) a compound that generates an acid or a radical by heat.

In the case of such a positive photosensitive resin composition, the mechanical strength, chemical resistance, adhesion, and the like of the obtained pattern or coating film can be further improved by further performing crosslinking and curing reaction.

Further, the present invention provides a pattern forming method including the steps of: (1) a step of coating the positive photosensitive resin composition on a substrate to form a photosensitive material coating film; (2) then, after the heating treatment, exposing the photosensitive material coating film with a high-energy ray or electron beam having a wavelength of 190-500 nm through a photomask; (3) and a step of developing the substrate with a developer of an alkaline aqueous solution.

In the pattern forming method of the present invention, a high resolution with which a fine pattern can be formed can be obtained.

In this case, it is further preferable to include: (4) and post-curing the coating film patterned by the development at a temperature of 100 to 300 ℃.

Such a pattern forming method can improve the crosslinking density of the coating film, remove the remaining volatile components, and improve the adhesion to the substrate, heat resistance, strength, and electrical characteristics.

The present invention also provides a photosensitive dry film having a structure in which a photosensitive resin layer having a film thickness of 5 to 100 μm is sandwiched between a support film and a protective film, wherein the composition for forming the photosensitive resin layer is the positive photosensitive resin composition.

In the photosensitive dry film of the present invention, a pattern can be easily formed on a substrate.

In addition, the present invention provides a method for manufacturing a photosensitive dry film, comprising the steps of: (i) a step of forming a photosensitive resin layer by continuously applying the positive photosensitive resin composition on a support film; (ii) a step of continuously drying the photosensitive resin layer; (iii) and further laminating the protective film on the photosensitive resin layer.

In such a method for producing a photosensitive dry film, the photosensitive dry film can be easily produced.

Further, the present invention provides a pattern forming method including the steps of: (i) a step of closely adhering the photosensitive resin layer exposed by peeling the protective film from the photosensitive dry film to the substrate; (ii) exposing the photosensitive resin layer with a high-energy ray or an electron beam having a wavelength of 190 to 500nm through the support film or through a photomask in a state where the support film is peeled; (iii) and a step of developing with a developer.

In the pattern forming method of the present invention, a fine pattern can be formed easily and high resolution can be obtained.

In this case, it is preferable that the method further comprises: (iv) and post-curing the coating film patterned by the development at a temperature of 100 to 300 ℃.

Such a pattern forming method can improve the crosslinking density of the coating film and can improve the adhesion to the substrate, heat resistance, strength, and electrical characteristics.

The present invention further provides a coating film for protecting an electric and electronic component, which is formed from a cured coating film obtained by curing the positive photosensitive resin composition.

The electrical and electronic component protective coating of the present invention is excellent in adhesion to a substrate, heat resistance, electrical characteristics, mechanical strength, and resistance to chemicals such as alkaline peeling solutions, and the semiconductor element to which the protective coating is applied is excellent in reliability, and particularly, can prevent the occurrence of cracks during a temperature cycle test.

Effects of the invention

As described above, the polymer of the present invention is soluble in an organic solvent which is widely used as a solvent for a positive photosensitive resin composition and is safe, and can provide a base resin for a photosensitive resin composition. In the pattern formation using the photosensitive resin composition containing the polymer of the present invention, development using an alkaline aqueous solution is possible, and since the polymer of the present invention is soluble in an alkaline aqueous solution, pattern deterioration such as residue such as scum or bottom-bottom difference (bottom き) can be suppressed at the bottom of the opened pattern, and resolution of a fine pattern can be performed.

Detailed Description

As described above, a polymer which is soluble in an organic solvent which is widely used as a solvent for a positive photosensitive resin composition and is safe and can be used as a base resin of an alkali-developable photosensitive resin composition has been demanded.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that, when a polymer comprising a polyamide, polyamideimide or polyimide structural unit selected from the group consisting of a polyamide, polyamideimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, a diamine, a tetracarboxylic dianhydride represented by the following general formula (3) and a dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (4) is used as a base resin for a photosensitive resin composition, the polymer is easily soluble in a widely used and safe organic solvent, is useful for the construction of a composition, and is soluble in a developer of an aqueous alkaline solution, and can be used in a positive photosensitive resin composition which can be developed with an aqueous alkaline solution, and that a fine pattern and a good pattern shape can be obtained by using the photosensitive resin composition The diamine includes at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2).

Further, it was found that: although the polymer is soluble in an alkaline aqueous solution, a coating film obtained by patterning and heating a photosensitive resin composition containing the polymer is excellent in resistance to a strongly alkaline plating release solution.

Further, it was found that: the protective coating obtained by patterning and heating using the photosensitive resin composition containing the polymer as a base resin is excellent in mechanical strength and adhesion. Namely, it was found that: the present invention has been completed by providing a cured coating film obtained by patterning using the above polymer as a base resin, which is excellent as a protective coating film for electric and electronic components and an insulating protective coating film.

That is, the present invention is a polymer having a polyamide, polyamideimide or polyimide structural unit, characterized in that the polymer is selected from the group consisting of a polyamide, polyamideimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor, the polymer comprises a reaction product of a diamine containing at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2) and at least one of a tetracarboxylic dianhydride represented by the following general formula (3) and a dicarboxylic acid or a dicarboxylic acid halide represented by the following general formula (4).

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

Wherein Z represents an alicyclic structure to which an alicyclic or aromatic ring having 3 to 20 carbon atoms is bonded or an alicyclic structure to which an alicyclic or aromatic ring containing or intervening hetero atoms is bonded, and A representsA hydroxyl group or a halogen atom, j represents 0 or 1, j represents 0, and represents that the phthalic anhydride structure in the general formula (3) is directly bonded to the cyclic structure Z, the benzoic acid structure in the general formula (4) is directly bonded to the cyclic structure Z, and when j represents 1, X represents₁、X₂Represents a divalent linking group.

The present invention will be described in detail below, but the present invention is not limited to these contents.

[ Polymer having Polyamide-imide-or polyimide-structural Unit ]

The polymer of the present invention has a polyamide, polyamideimide, or polyimide structural unit, and is selected from the group consisting of polyamides, polyamideimides, polyimides, polyimide precursors, polybenzoxazoles, and polybenzoxazole precursors, and the polymer comprises a reaction product of a diamine comprising at least one of a diamine represented by the following general formula (1) and a diamine represented by the following general formula (2), and a tetracarboxylic dianhydride represented by the following general formula (3) and a dicarboxylic acid or a dicarboxylic acid halide represented by the following general formula (4). The polymer of the present invention is not particularly limited as long as the above conditions are satisfied.

The polymer is used as a base resin of a positive photosensitive resin composition, can improve mechanical strength and glass transition temperature, is easily soluble in widely used and safe organic solvents, and is soluble in a developer of an alkaline aqueous solution.

Since the polymer of the present invention is prepared by forming an amide structural unit or an imide structural unit in advance during the synthesis of the polymer, a reaction such as an imide ring-closure reaction is not required in the heat curing after the pattern formation of the photosensitive resin composition using the polymer, and thus a high heating temperature such as an imidization reaction is not required. Further, since an amide structural unit or an imide structural unit is formed, a release reaction does not occur, and there is an advantage that film shrinkage during heat treatment is small.

Generally, as a means for improving physical properties after curing of the obtained pattern, particularly mechanical strength such as tensile strength, or a method for increasing Tg, a method of introducing a biphenyl structural unit or a terphenyl structural unit into a polymer is known. However, the polymer having these structural units introduced therein is not preferable because the solubility in widely used and safe organic solvents is significantly deteriorated and the polymer is a polymer which is soluble only in N-methyl-2-pyrrolidone or a polymer which is insoluble in any organic solvent. On the other hand, the polymer of the present invention is soluble in a widely used and safe organic solvent as a solvent for a photosensitive resin composition without the need for the above-mentioned means and method, and can provide a positive photosensitive resin composition having a high glass transition temperature which is excellent in mechanical strength and heat resistance to a film cured after pattern formation.

The alicyclic structure Z of the general formulae (3) and (4) of the polymer of the present invention is preferably the following general formula (11) or (12).

[ chemical formula 30]

Wherein the dotted line represents a bond, and k represents an integer of 0 or 1 or more; y is₂Represents a divalent group selected from any one of the following general formulae (13), (14), (15), and (16); when k is 1, Y₁Represents a divalent group selected from any one of the following general formulae (17), (18), (19), and (20); when k is 2 or more, Y₁Represents the following general formula (17); r¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Bonded to each other to form an alicyclic or aromatic ring.

[ chemical formula 31]

Wherein the dotted line represents a bond, R⁷Represents methyl, ethyl, straight chain, branched chain or cyclic alkyl with 3-12 carbon atoms。

[ chemical formula 32]

Wherein the dotted line represents a bond, R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Bonded to each other to form an alicyclic structure or an aromatic ring structure; m and p represent 0 or an integer of 1 to 9; n represents 0 or 1; y is₃Represents a divalent group selected from any one of the general formulae (13), (14), (15), (16), (17), (18), (19), and (20).

Further, it is preferable that: the alicyclic structure Z of the general formula (3) of the polymer of the present invention is a tetracarboxylic dianhydride selected from any one of the general formulae (Z-1) and (Z-2); the alicyclic structure Z of the general formula (4) is any one or more selected from dicarboxylic acids and dicarboxylic acid halides of any one of the formulae (Z-3) to (Z-8).

[ chemical formula 33]

[ chemical formula 34]

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

[ chemical formula 38]

[ chemical formula 39]

[ chemical formula 40]

Wherein the dotted line represents a bond, R¹、R²、R³、R⁴、R⁵、R⁶The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R¹、R²、R³、R⁴、R⁵、R⁶Bonded to each other to be an alicyclic or aromatic ring; r⁷Represents a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms; r⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵The same or different substituents are represented by a hydrogen atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms, or R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵Respectively bonded to form an alicyclic structure or an aromatic ring structure.

When the alicyclic structure Z of the general formula (3) is a tetracarboxylic dianhydride selected from the following general formulae (Z-1) and (Z-2), it can be easily obtained or synthesized. The alicyclic structure Z in (4) is selected from dicarboxylic acids represented by any one of the following formulae (Z-3) to (Z-8), and can be easily obtained or synthesized as well. Dicarboxylic acid halides can be readily obtained by reacting these dicarboxylic acids with halogenating agents.

Among the alicyclic structures Z of the above general formulae (3) and (4), preferable structures that can be represented by the above general formula (11) include the following structures. However, it is not limited thereto.

[ chemical formula 41]

In the formula, the dotted line represents a bond.

Among the alicyclic structures Z of the above general formulae (3) and (4), preferable structures that can be represented by the above general formula (12) include the following structures. However, it is not limited thereto.

[ chemical formula 42]

In the formula, the dotted line represents a bond.

In the general formulae (3) and (4), when j is 0, the phthalic anhydride structure in the general formula (3) and the cyclic structure Z are directly connected, and the benzoic acid structure in the general formula (4) and the cyclic structure Z are directly connected, so that the phthalic anhydride structure or the benzoic acid structure is directly bonded to the dotted line portion of the bond representing the above-mentioned structures, and preferable examples thereof include the following general formulae (3-1), (3-2), (3-3), (4-1) to (4-6).

[ chemical formula 43]

[ chemical formula 44]

Wherein Z, A is the same as described above.

Among the above general formula (3), the above general formula (3-1) is preferable in view of the synthetic method or the ease of obtaining. In the general formula (4), the general formula (4-1) is preferable in view of the synthetic method and the ease of obtaining.

In the general formulae (3) and (4), when j is 1, X₁、X₂Represents a divalent linking group as linking group X₁、X₂Preferred examples of the structure (b) include groups represented by the following general formulae (5), (6), (7), (8), (9) and (10).

[ chemical formula 45]

In the formula, the dotted line represents a bond.

In the general formula (3), when j is 1, the following structure can be specifically mentioned as a preferable structure. However, it is not limited thereto.

[ chemical formula 46]

Wherein Z is the same as described above.

Among these general formulae (3-4) to (3-9), the general formulae (3-5), (3-7) and (3-8) are preferable in view of the synthetic method and the ease of obtaining. Particularly preferred are (3-5) and (3-7).

In the general formula (4), when j is 1, the following structure can be specifically mentioned as a preferable structure. However, it is not limited thereto.

[ chemical formula 47]

Among these general formulae (4-7) to (4-12), the general formulae (4-8), (4-10) and (4-11) are preferable in view of the synthetic method and the ease of obtaining. Particularly preferred are (4-8) and (4-10).

Further, the general formula (1) is preferably a diamine represented by the following general formula (21).

[ chemical formula 48]

When the general formula (1) is the diamine represented by the general formula (21), a developer of an alkaline aqueous solution can be used in the pattern formation and the developing step. The use of a developer containing an aqueous alkali solution makes it easy to measure and control the dissolution rate of the base resin in the developer containing an aqueous alkali solution, and thus contributes to the improvement of the resolution of the photosensitive resin composition.

Then, the polymer containing a unit of the tetracarboxylic acid diester represented by the general formula (22) is more easily soluble in a widely used and safe organic solvent.

[ chemical formula 49]

Wherein W1 is a 4-valent organic group, R¹⁶Is represented by the following general formula (23).

[ chemical formula 50]

Wherein the dotted line represents a bond, V₁Is an (r +1) -valent organic group, Rf is an aromatic group which may be substituted by a linear, branched or cyclic alkyl group or alkyl group having 1 to 20 carbon atoms in which some or all of the hydrogen atoms are substituted by fluorine atoms, r represents 1,2 or 3, and q represents 0 or 1.

In this case, R in the above general formula (22) is preferably R¹⁶Is an organic group selected from any one of the groups represented by the following general formulae (24), (25), (26) and (27).

[ chemical formula 51]

[ chemical formula 52]

[ chemical formula 53]

[ chemical formula 54]

Wherein the dotted line represents a bond; rf is the same as above, Ra and Rb are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, V₂And V₃Is a linear or branched alkylene group having 1 to 6 carbon atoms, q1 represents an integer of 0 to 6, q2 represents an integer of 1 to 6, q3 represents an integer of 0 to 6, q4 represents an integer of 1 to 6, q5 represents an integer of 0 to 6, q6 represents 0 or 1, and q7 represents 0 or 1.

Further, R in the above general formula (22) is preferably R¹⁶Is a group represented by the following general formula (23-1).

[ chemical formula 55]

＊------CH₂-CH₂-Rf (23-1)

Wherein the dotted line represents a bond; rf is the same as described above.

Among the organic groups represented by the above general formula (24), the following organic groups can be specifically mentioned as organic groups that can be preferably used. However, it is not limited thereto.

[ chemical formula 56]

[ chemical formula 57]

In the formula, the dotted line represents a bond.

Among the organic groups represented by the above general formula (25), the following organic groups can be specifically mentioned as organic groups that can be preferably used. However, it is not limited thereto.

[ chemical formula 58]

[ chemical formula 59]

[ chemical formula 60]

[ chemical formula 61]

Wherein the dotted line represents a bond; n2 represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.

Among the organic groups represented by the above general formula (26), the following organic groups can be specifically mentioned as organic groups that can be preferably used. However, it is not limited thereto.

[ chemical formula 62]

[ chemical formula 63]

[ chemical formula 64]

[ chemical formula 65]

[ chemical formula 66]

[ chemical formula 67]

Wherein the dotted line represents a bond; n4 represents an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and most preferably 1.

Among the organic groups represented by the above general formula (27), the following organic groups can be specifically mentioned as organic groups that can be preferably used. However, it is not limited thereto.

[ chemical formula 68]

In the formula, the dotted line represents a bond.

Wherein the polymer of the present invention containing a unit of a tetracarboxylic acid diester represented by the general formula (22) undergoes a ring-closure reaction of imidization in a structural unit of a polyimide precursor in heating for post-curing after patterning using a photosensitive resin composition for a base resin, but in this case, R is introduced¹⁶The film was removed from the system by peeling, and the film thickness of the formed film was observed to decrease. Therefore, in order to minimize the film reduction at the time of post-curing, R is more preferable¹⁶Its molecular weight is small.

The introduction of the units of the tetracarboxylic acid diester into the polymer of the present invention can be carried out, for example, by: an excess amount of a diamine containing at least one of the diamines represented by the general formulae (1) and (2) is used, and the diamine is reacted with a tetracarboxylic dianhydride represented by the general formula (3) to synthesize an amic acid oligomer having an amino group at the terminal, and then the terminal amino group of the amic acid oligomer is reacted with a tetracarboxylic diester compound represented by the general formula (22). Alternatively, the unit of the tetracarboxylic acid diester may be introduced into the polymer by using an excess amount of the diamine and reacting the diamine with at least one of the dicarboxylic acids represented by the general formula (4) or the dicarboxylic acid halides in the same manner as described above.

A preferred method for producing the tetracarboxylic acid diester compound represented by the general formula (22) is a method in which R is introduced by reacting a tetracarboxylic dianhydride represented by the following general formula (28) with a compound having a hydroxyl group at the terminal represented by the following general formula (29) in the presence of a basic catalyst such as pyridine¹⁶The method of (1).

[ chemical formula 69]

In the formula, W1 is the same as described above.

[ chemical formula 70]

In the formula, V₁Rf, q and r are the same as above.

Examples of suitable tetracarboxylic dianhydrides represented by the general formula (28) include aromatic acid dianhydrides, alicyclic acid dianhydrides, and aliphatic acid dianhydrides. Examples of the aromatic acid dianhydride include pyromellitic dianhydride, 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4' -biphenyltetracarboxylic dianhydride, 2,3,2 ', 3' -biphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -terphenyltetracarboxylic dianhydride, 3,3 ', 4, 4' -oxophthalic dianhydride, 2,3,3 ', 4' -oxophthalic dianhydride, 2,3,2 ', 3' -oxophthalic dianhydride, diphenylsulfone-3, 3 ', 4, 4' -tetracarboxylic dianhydride, benzophenone-3, 3 ', 4, 4' -tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, 1,4- (3, 4-dicarboxyphenoxy) benzene dianhydride, p-phenylene bis (trimellitic acid monoester anhydride), bis (1, 3-dioxo-1, 3-dihydroisobenzofuran-5-carboxylic acid) 1, 4-phenylene ester, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1,2,5, 6-naphthalene tetracarboxylic acid dianhydride, 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorene dianhydride, 2,3,5, 6-pyridinetetracarboxylic dianhydride, 3,4,9, 10-perylenetetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 2-bis (4- (3, 4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 1, 6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1, 6-bistrifluoromethylpyromellitic dianhydride, 2 '-bis (trifluoromethyl) -4, 4' -bis (3, 4-dicarboxyphenoxy) biphenyl dianhydride, 2 '-bis [ (dicarboxyphenoxy) phenyl ] propane dianhydride, 2' -bis [ (dicarboxyphenoxy) phenyl ] hexafluoropropane dianhydride, or an alkyl group, an alkoxy group, An acid dianhydride compound obtained by substituting an aromatic ring of the above compound with a halogen atom, etc., but the present invention is not limited thereto.

Examples of the alicyclic acid dianhydride include 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 1,2,4, 5-cyclohexanetetracarboxylic dianhydride, 1,2,4, 5-cyclopentanetetracarboxylic dianhydride, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cycloheptanetetracarboxylic dianhydride, 2,3,4, 5-tetrahydrofurantetracarboxylic dianhydride, 3, 4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3, 5-tricarboxycyclopentylacetic dianhydride, 1,2,3, 4-tricarboxycyclopentylacetic dianhydride, 3, 4-dicarboxy-1, 2,3, 4-tetrahydro-1-naphthalene succinic dianhydride, bicyclo [3,3,0]Octane-2, 4,6, 8-tetracarboxylic dianhydride, bicyclo [4,3, 0]]Nonane-2, 4,7, 9-tetracarboxylic dianhydride, bicyclo [4,4, 0]]Decane-2, 4,7, 9-tetracarboxylic dianhydride, bisCyclo [4,4,0]Decane-2, 4,8, 10-tetracarboxylic dianhydride, tricyclo [6,3,0^2,6]Undecane-3, 5,9, 11-tetracarboxylic dianhydride, bicyclo [2, 2] dianhydride]Octane-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2, 2]]Octyl-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, bicyclo [2,2, 1-]Heptanetetracarboxylic dianhydride, bicyclo [2,2, 1]]Heptane-5-carboxymethyl-2, 3, 6-tricarboxylic dianhydride, 7-oxabicyclo [2,2,1]Heptane-2, 4,6, 8-tetracarboxylic dianhydride, octahydronaphthalene-1, 2,6, 7-tetracarboxylic dianhydride, decatetrahydroanthracene-1, 2,8, 9-tetracarboxylic dianhydride, 3', 4,4 ' -bicyclohexane tetracarboxylic dianhydride, 3 ', 4,4 ' -oxobicyclohexane tetracarboxylic dianhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, and "RIKACID" (registered trademark) BT-100 (trade name, manufactured by New japan chemical co., ltd.) and derivatives thereof, or an acid dianhydride compound obtained by substituting an alicyclic ring of the above compound with an alkyl group, an alkoxy group, a halogen atom, or the like, but the present invention is not limited thereto.

Examples of the aliphatic acid dianhydride include, but are not limited to, 1,2,3, 4-butanetetracarboxylic dianhydride, 1,2,3, 4-pentanetetracarboxylic dianhydride, and derivatives thereof.

These aromatic acid dianhydrides, alicyclic acid dianhydrides or aliphatic acid dianhydrides may be used alone or in combination of two or more.

The reaction of the tetracarboxylic dianhydride represented by the general formula (28) with the compound having a hydroxyl group at the terminal represented by the general formula (29) can be carried out by stirring, dissolving and mixing the tetracarboxylic dianhydride represented by the general formula (28) and the compound having a hydroxyl group at the terminal represented by the general formula (29) in a reaction solvent at a reaction temperature of 20 to 50 ℃ for 4 to 10 hours in the presence of a basic catalyst such as pyridine, thereby carrying out a half-esterification reaction of the acid dianhydride and obtaining a desired solution in which the tetracarboxylic diester compound represented by the general formula (28) is dissolved in the reaction solvent.

The tetracarboxylic acid diester compound obtained may be isolated, or the solution obtained may be used as it is in the next step described below, i.e., in the reaction with the diamine.

The reaction solvent is preferably a solvent that sufficiently dissolves the tetracarboxylic acid diester compound and the polymer having a structural unit of the polyimide precursor obtained by the subsequent polycondensation reaction of the tetracarboxylic acid diester compound and the diamine, and examples thereof include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, and γ -butyrolactone. Further, ketones, esters, lactones, ethers, halogenated hydrocarbons, and the like can be used, and specific examples thereof include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, 1, 4-dichlorobutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, toluene, xylene, and the like. These solvents may be used alone or in combination of two or more, as required.

The polymer of the present invention may have a structure containing another diamine represented by the following general formula (30) and obtained by reacting a diamine containing at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2), a tetracarboxylic dianhydride represented by the general formula (3), and a dicarboxylic acid or a dicarboxylic acid halide represented by the general formula (4).

[ chemical formula 71]

H₂N-T-NH₂(30)

T in the structural unit (30) is a divalent organic group, and is not particularly limited as long as it is a divalent organic group, preferably a divalent organic group having 6 to 40 carbon atoms, and more preferably a cyclic organic group containing 1 to 4 substituted aromatic rings or aliphatic rings, or an aliphatic group or siloxane group having no cyclic structure. Further preferable T is represented by the following formula (31) or (32). One or a combination of two or more of T structures may be used.

[ chemical formula 72]

In the formula, the dotted line represents a bond with an amino group.

[ chemical formula 73]

Wherein the dotted line represents a bond with an amino group, R¹⁷Each independently represents a methyl group, an ethyl group, a propyl group, an n-butyl group or a trifluoromethyl group, and t represents an integer of 2 to 20.

The polymer of the present invention may have a structure containing another tetracarboxylic anhydride represented by the following general formula (33) and obtained by reacting a diamine containing at least one of a diamine represented by the above general formula (1) and a diamine represented by the above general formula (2) with at least one of a tetracarboxylic dianhydride represented by the above general formula (3) and a dicarboxylic acid or a dicarboxylic acid halide represented by the above general formula (4).

[ chemical formula 74]

W in the formula of the tetracarboxylic dianhydride represented by the general formula (33)₂The same tetravalent organic group as W1 in the formula of the above general formula (28) is preferable. Further, as a preferable example of the tetracarboxylic dianhydride represented by the general formula (33), tetracarboxylic acid anhydride represented by the general formula (28) can be mentioned.

The polymer of the present invention may further contain a structure containing another dicarboxylic acid or dicarboxylic acid halide represented by the following general formula (34) and obtained by reacting a diamine containing at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2) with at least one of the tetracarboxylic dianhydride represented by the general formula (3) and the dicarboxylic acid or dicarboxylic acid halide represented by the general formula (4).

[ chemical formula 75]

Wherein A is the same as described above.

Wherein U is a divalent organic group having an aliphatic chain length structure of 4 to 40 carbon atoms, or a divalent organic group of an alicyclic aliphatic group or an aromatic group. Further preferred is a divalent organic group represented by the following formula (34-1). In addition, the structure of U may be one, or a combination of two or more.

[ chemical formula 76]

In the formula, R¹⁸、R¹⁹Each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, s is an integer of 1 to 30, and the dotted line represents a bond with a carboxyl group or a carboxyl halide group (カルボキシハライド group).

When U in the dicarboxylic acid or dicarboxylic acid halide represented by the general formula (34) is a divalent organic group having an aliphatic chain length structure, the cured film of the photosensitive resin composition using the polymer of the present invention as a base resin is preferably high in mechanical strength, particularly elongation.

Examples of the dicarboxylic acid compound represented by the above general formula (34) include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,6, 6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorsebacic acid, 1, 9-azelaic acid, 1-azelaic acid, and 3-dimethylglutaric acid, Dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, tridecanedioic acid, hentriacontanedioic acid, diglycolic acid, etc.

Further, examples of the dicarboxylic acid compound having an aromatic ring include phthalic acid, isophthalic acid, terephthalic acid, 4 '-diphenyl ether dicarboxylic acid, 3' -diphenyl ether dicarboxylic acid, 4 '-diphenyl dicarboxylic acid, 3' -diphenyl dicarboxylic acid, 4 '-benzophenonedicarboxylic acid, 3' -benzophenonedicarboxylic acid, 4 '-hexafluoroisopropylidenedibenzoic acid, 4' -dicarboxyldiphenylamide, 1, 4-phenylenediacetic acid, bis (4-carboxyphenyl) sulfide, 2-bis (4-carboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, bis (4-carboxyphenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2-bis (p-carboxyphenyl) propane, 2, 6-naphthalenedicarboxylic acid, and the like, but is not limited thereto. Further, these dicarboxylic acid compounds may be used alone or in combination.

[ Polymer having Polyamide, polyamideimide, polyimide structural Unit and Process for producing the Polymer ]

(Polyamide, polyamideimide, polyimide structural Unit)

The polymer of the present invention is characterized by having a polyamide, polyamideimide, or polyimide structural unit obtained by reacting a diamine containing at least one of a diamine represented by the above general formula (1) and a diamine represented by the above general formula (2) with at least one of a tetracarboxylic dianhydride represented by the above general formula (3) and a dicarboxylic acid or dicarboxylic acid halide represented by the below general formula (4).

The polyamide structural units include those represented by the following general formulae (35) and (36) obtained by reacting a diamine containing at least one of the diamines represented by the general formula (1) and the diamines represented by the general formula (2) with at least one of the dicarboxylic acids represented by the general formula (4) or the dicarboxylic acid halides.

[ chemical formula 77]

The polyimide structural units include polyamide structural units represented by the following general formulae (37) and (38) obtained by reacting a diamine containing at least one of the diamines represented by the general formula (1) and the diamines represented by the general formula (2) with a tetracarboxylic dianhydride represented by the general formula (3).

[ chemical formula 78]

As the polyamideimide structural unit, the following polyamideimide structural units are provided: the polyimide resin composition has a structure comprising at least one of structural units of the general formulae (35) and (36) and at least one of structural units of the general formulae (37) and (38) obtained by simultaneously reacting a diamine comprising at least one of a diamine represented by the general formula (1) and a diamine represented by the general formula (2) with a tetracarboxylic dianhydride represented by the general formula (3) and at least one of a dicarboxylic acid represented by the general formula (4) and a dicarboxylic acid halide represented by the general formula (4), or by adding at least one of a dicarboxylic acid represented by the general formula (4) and a dicarboxylic acid halide to the resulting polyimide resin composition and then reacting the resulting mixture.

(Process for producing Polyamide, polyamideimide, polyimide structural Unit)

The polymer of the polyamide structural unit containing the above structural unit (35) or (36) can be obtained by: after the reaction in the presence of a dehydration condensation agent or the conversion into an acid halide (acid ハライド compound) using a halogenating agent, a dicarboxylic acid in which A in the formula (4) is a hydroxyl group is reacted with a diamine, or a dicarboxylic acid halide in which A in the formula (4) represents a halogen atom is used and reacted with a diamine.

Among them, there is a method of using a chlorinating agent such as thionyl chloride or oxalic acid dichloride as a halogenating agent for converting the dicarboxylic acid into an acid halide, converting the acid halide into an acid chloride (acid salt), and reacting the acid chloride with a diamine to synthesize the compound.

In the reaction of converting the above dicarboxylic acid into an acid chloride using a chlorinating agent, a basic compound may be used. Examples of the basic compound include pyridine, dimethylaminopyridine, 1, 8-diazacyclo [5.4.0] undec-7-ene, 1, 5-diazacyclo [4.3.0] nona-5-ene and the like.

In this case, as the solvent used in the method of passing an acid chloride or the solvent used in the reaction for obtaining a polyamide structure by using a dicarboxylic acid halide in which a in the above general formula (4) represents a halogen atom, which is prepared in advance, it is preferable to use a solvent in which a polymer having a polyamide structure obtained by a polycondensation reaction of an acid chloride and a dicarboxylic acid halide with a diamine is favorably dissolved, and specific examples thereof include N-methyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoric triamide, γ -butyrolactone, and the like. In addition to the polar solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, and the like can be used. Examples thereof include acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1, 2-dichloroethane, 1, 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. These organic solvents may be used alone or in combination of two or more.

The diamine compound is obtained by reacting a diamine containing at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2) with a dicarboxylic acid in which a is a hydroxyl group in the general formula (4) in the presence of a dehydration condensation agent. That is, the dicarboxylic acid in which A in the formula of the above general formula (4) is a hydroxyl group is used in the reaction in a state of being dissolved in the same reaction solvent as described above, and a known dehydration condensation agent (for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1, 2-dihydroquinoline, 1-carbonyldioxo-di-1, 2, 3-benzotriazole, N' -disuccinimidyl carbonate, or the like) is added and mixed to the reaction solution under ice cooling to prepare a dicarboxylic acid compound in which A in the formula of the above general formula (4) is a hydroxyl group as a polyacid anhydride, and then a solution in which the diamine represented by the above general formula (1) and the diamine represented by the general formula (2) are dissolved or dispersed in another solvent is added dropwise thereto to conduct polycondensation, thereby obtaining a dicarboxylic acid compound containing a structural unit (35) and a structural unit (2), (36) The polymer of (1).

In the production of the polymer containing a polyamide structural unit of the structural unit (35) or (36), a polymer containing a polyamide structural unit of the present invention can be obtained by using a diamine other than the diamine represented by the general formula (1) and the diamine represented by the general formula (2), for example, another diamine represented by the general formula (30).

In addition, in the preparation of the polymer containing a polyamide structural unit of the structural unit (35) or (36), a polymer containing a polyamide structural unit of the present invention can be obtained without fail by using a dicarboxylic acid or a dicarboxylic acid halide other than any of the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (4), that is, another dicarboxylic acid or dicarboxylic acid halide represented by the general formula (34).

Next, a method for producing the polyimide structures represented by the general formulae (37) and (38) will be described. The polyimide structures represented by the general formulae (37) and (38) are produced by first synthesizing an amic acid by reacting a diamine comprising at least one of the diamines represented by the general formula (1) and the diamines represented by the general formula (2) with a tetracarboxylic dianhydride represented by the general formula (3), and then dehydrating the amic acid by heating.

The preparation of the polyimide structure can be carried out by: dissolving diamine in a high boiling point and high polarity solvent such as gamma-butyrolactone and N-methyl-2-pyrrolidone, adding an acid anhydride, reacting at 0 to 80 ℃, preferably 10 to 50 ℃ to produce an amic acid, adding a nonpolar solvent such as xylene, heating to 100 to 200 ℃, preferably 130 to 180 ℃, and carrying out an imidization reaction while removing water from the reaction system.

In the preparation of the polymer containing the polyimide structure represented by the general formulae (37) and (38), a polymer containing a polyimide structural unit of the present invention can be obtained without limitation by using a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the general formula (3), that is, the tetracarboxylic dianhydride represented by the general formula (33).

In addition, in the production of the polymer containing the polyimide structure represented by the above general formulae (37) and (38), the polymer containing the polyimide structural unit of the present invention can be obtained by using a diamine other than the diamine containing at least one of the diamine represented by the above general formula (1) and the diamine represented by the above general formula (2), that is, for example, another diamine represented by the above general formula (30).

As a method for producing a polymer containing a polyamideimide structure having at least one or more of the structures of the general formulae (35) and (36) and at least one or more of the structures of the general formulae (37) and (38), a polyamideimide structure can be formed by reacting a diamine containing at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2) with a tetracarboxylic dianhydride represented by the general formula (3) to form an amic acid, and dehydrating a dicarboxylic acid in which a in the formula of the general formula (4) is a hydroxyl group by heating in the same system as the amic acid.

As another method for producing a polyamide-imide structure, in the production of the polymer containing a polyimide structure represented by the above general formulae (37) and (38), an amic acid oligomer having an amino group at the terminal is synthesized by reacting a tetracarboxylic dianhydride represented by the above general formula (3) with an excess of a diamine containing at least one of a diamine represented by the above general formula (1) and a diamine represented by the above general formula (2), and then the amino group at the terminal of the amic acid oligomer is reacted with a dicarboxylic acid represented by the above general formula (4) by the same method as the production method for producing the above polyamide structure, whereby a polyamide-imide structure can be obtained.

In the same manner as described above, in the production of a polymer containing a polyamideimide structure, diamines other than the diamine represented by the above general formula (1) and the diamine represented by the above general formula (2), for example, other diamines represented by the above general formula (30), may be used together. Further, tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the general formula (3), that is, tetracarboxylic dianhydrides represented by the general formula (33), may be used together, and dicarboxylic acids or dicarboxylic acid halides other than any of the dicarboxylic acids or dicarboxylic acid halides represented by the general formula (4), that is, other dicarboxylic acids or dicarboxylic acid halides represented by the general formula (34), may be used together.

(introduction of a Unit of the tetracarboxylic acid diester represented by the general formula (22))

Next, a method of introducing a unit of the tetracarboxylic acid diester represented by the above general formula (22) is shown. A method for introducing a unit of a tetracarboxylic acid diester represented by the general formula (22) into a polymer characterized by comprising a step of reacting a tetracarboxylic dianhydride represented by the general formula (3) with an excess amount of a diamine containing at least one of a diamine represented by the general formula (1) and a diamine represented by the general formula (2) to synthesize an amic acid oligomer having an amino group at the terminal, and a step of reacting the terminal amino group of the amic acid oligomer with a dicarboxylic acid represented by the general formula (22) by the same method as the method for producing the polyamide structure, thereby introducing a unit of a tetracarboxylic acid diester represented by the general formula (22), wherein the polymer comprises a polyamide obtained by reacting a diamine with at least one of a tetracarboxylic dianhydride represented by the general formula (3) and a dicarboxylic acid represented by the general formula (4) or a dicarboxylic acid halide, A polyamide imide and a polyimide structural unit, wherein the diamine contains at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2).

Alternatively, the unit of the tetracarboxylic acid diester represented by the general formula (22) can be introduced by reacting an excess of a diamine containing at least one of the diamine represented by the general formula (1) and the diamine represented by the general formula (2) with at least one of the dicarboxylic acid represented by the general formula (4) or the dicarboxylic acid halide to synthesize an amide oligomer having an amino group at the terminal, and then reacting the amino group at the terminal of the amide oligomer with the tetracarboxylic acid diester compound represented by the general formula (22) by the same method as the method for producing the polyamide structure.

(introduction of molecular weight of Polymer and end-capping agent)

The polymer of the present invention is characterized by having a polyamide, polyamideimide, or polyimide structural unit obtained by reacting a diamine containing at least one of the diamine represented by the above general formula (1) and the diamine represented by the general formula (2) of the present invention with at least one of a tetracarboxylic dianhydride represented by the above general formula (3) and a dicarboxylic acid or dicarboxylic acid halide represented by the above general formula (4), and the polymer preferably has a molecular weight of 5,000 to 100,000, more preferably 7,000 to 30,000. When the molecular weight is 5,000 or more, a photosensitive resin composition using the above polymer as a base resin can be easily formed into a film with a desired film thickness on a substrate, and when the molecular weight is 100,000 or less, the viscosity of the photosensitive resin composition does not increase significantly, and there is no possibility that the film cannot be formed.

For the purpose of controlling the molecular weight of the polycondensation reaction and suppressing gelation, which is a change in molecular weight with time, of the resulting polymer, both ends of the polymer of the present invention may be capped with a terminal capping agent. Examples of the terminal-capping agent to be reacted with the acid dianhydride include monoamines and monoalcohols. Examples of the terminal-capping agent to be reacted with the diamine compound include acid anhydrides, monocarboxylic acids, monoacid chloride compounds, mono-active ester compounds, dicarbonates, vinyl ethers, and the like. Further, by reacting the terminal-blocking agent, various organic groups can be introduced as terminal groups.

As the monoamine used as the end-capping agent for the acid anhydride group, aniline, 5-amino-8-quinolinol, 4-amino-8-quinolinol, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, etc., can be mentioned, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-aminonaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, melamine monoamide (アメライド), 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 5-amino-8-mercaptoquinoline, 4-amino-5-aminonaphthalene, 4-aminonaphthalene, 2-aminonaphthalene, 5-amino-5-aminonaphthalene, 4-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4, 6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 1-mercapto-5-aminonaphthalene, 1-mercapto-amino-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminothiophenol, 3-aminothiophenol, 4-amino, 3-ethynylaniline, 4-ethynylaniline, 2, 4-diacetylenylaniline, 2, 5-diacetylenylaniline, 2, 6-diacetylenylaniline, 3, 4-diacetylenylaniline, 3, 5-diacetylenylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 3-ethynyl-4-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3, 5-diacetyl-1-aminonaphthalene, 3, 5-diacetyl-2-aminonaphthalene, 3, 6-diacetyl-1-aminonaphthalene, 3, 6-diacetyl-2-aminonaphthalene, 3, 7-diacetyl-1-aminonaphthalene, 3, 7-diacetyl-2-aminonaphthalene, 4, 8-diacetyl-1-aminonaphthalene, 4, 8-diacetyl-2-aminonaphthalene, and the like, but are not limited thereto. One of them may be used alone, or two or more of them may be used simultaneously.

Further, as the monohydric alcohol used as the end-capping agent for the terminal of the acid anhydride group, there may be mentioned methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1-nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecanol, 2-undecanol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2-tridecanol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-heptadecanol, 1-octadecanol, 2-octadecanol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4, 4-trimethyl-1-hexanol, 2, 6-dimethyl-4-heptanol, 2-methyl-1-heptanol, 1-octadecanol, 2-methyl-1-butanol, 2-propyl-1-pentanol, 2-ethyl-1-hexano, Isononyl alcohol, 3, 7-dimethyl-3-octanol, 2, 4-dimethyl-1-heptanol, 2-heptylundecanol, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether cyclopentanol, cyclohexanol, cyclopentane monomethyl ether, tricyclodecane monomethyl ether, norborneol (norbonenol), terpineol, etc., but is not limited thereto. These monohydric alcohols may be used singly or in combination of two or more.

Examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and mono-active ester compound used as the end-capping agent for the amino terminal include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride and 3-hydroxyphthalic anhydride; 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 2-carboxynaphthalene, 4-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 2, 4-diacetylenebenzoic acid, 2, 5-diacetylenebenzoic acid, 2, 6-diacetylenebenzoic acid, 3, 4-diacetylenebenzoic acid, 3, 5-diacetylenebenzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 2-ethynyl-1-naphtho, Monocarboxylic acids such as 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, and 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds obtained by acid-chlorinating carboxyl groups thereof; and a monocarboxylic acid chloride compound obtained by acid chlorination of a monocarboxylic acid group of a dicarboxylic acid such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2, 3-dicarboxylic acid, 1, 2-dicarboxylnaphthalene, 1, 3-dicarboxylnaphthalene, 1, 4-dicarboxylnaphthalene, 1, 5-dicarboxylnaphthalene, 1, 6-dicarboxylnaphthalene, 1, 7-dicarboxylnaphthalene, 1, 8-dicarboxylnaphthalene, 2, 3-dicarboxylnaphthalene, 2, 6-dicarboxylnaphthalene, 2, 7-dicarboxylnaphthalene, etc.; and an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2, 3-dicarboximide.

Examples of the dicarbonate compound used as the end-capping agent for the amino terminal include di-tert-butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

Examples of the vinyl ether compound used as the blocking agent for the amino terminal include butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, benzyl vinyl ether, and the like.

Examples of other compounds used as the blocking agent for the amino terminal include chloroformates such as benzoyl chloride, fluorenylmethyl chloroformate, 2,2, 2-trichloroethyl chloroformate, tert-butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate and isopropyl chloroformate, isocyanate compounds such as butyl isocyanate, 1-naphthyl isocyanate, octadecyl isocyanate and phenyl isocyanate, and methanesulfonic chloride and p-toluenesulfonic chloride.

The introduction ratio of the end-capping agent at the acid anhydride group end is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, and further preferably 5 to 20 mol% with respect to the tetracarboxylic dianhydride component represented by the general formulae (3) and (33) or the carboxylic acid component represented by the general formulae (4) and (34). The introduction ratio of the end-capping agent at the amino terminal is preferably in the range of 0.1 to 100 mol%, and particularly preferably 5 to 90 mol% with respect to the diamine component represented by the general formula (30) containing at least one of the diamines represented by the general formula (1) and the diamines represented by the general formula (2). In addition, a plurality of different terminal groups can be introduced by reacting a plurality of terminal blocking agents.

[ photosensitive resin composition ]

Next, a photosensitive resin composition comprising the polymer of the present invention as a base resin will be described. In the present invention, a positive photosensitive resin composition can be obtained by using the polymer of the present invention as a base resin.

[ Positive photosensitive resin composition ]

First, a positive photosensitive resin composition capable of alkali development in a photosensitive resin composition containing the polymer of the present invention as a base resin will be described. The positive photosensitive resin composition of the present invention is not limited to these.

The positive photosensitive resin composition of the present invention contains: (A) the polymer of the present invention; (B) a photosensitizer which generates an acid by light, which is a compound having a quinonediazide structure; (D) a solvent.

The positive photosensitive resin composition of the present invention, that is, the positive photosensitive resin composition, may further contain the following component (C).

(C) And a crosslinking agent which is one or two or more selected from the group consisting of an amino condensate obtained by modifying formaldehyde or formaldehyde-alcohol, a phenol compound having an average of 2 or more methylol groups or alkoxymethyl groups in 1 molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).

[ chemical formula 79]

Wherein the dotted line represents a bond, Rc represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

The alkali solubility of the positive photosensitive composition of the present invention can be described by the number of moles of phenolic hydroxyl groups in 100g of the diamine containing at least one of the diamine represented by the above general formula (1) and the diamine represented by the general formula (2) in the component (a). That is, the molar number of the phenolic hydroxyl groups in 100g of the component (A) is preferably 0.10mol or more and 0.40mol or less, more preferably 0.20mol or more and 0.35mol or less, and most preferably 0.25mol or more and 0.35mol or less. When the number of moles of the phenolic hydroxyl group is 0.10mol or more, a desired alkaline dissolution rate can be obtained with respect to a developer which is an alkaline aqueous solution, and at the time of pattern formation, there is no possibility that an obstacle is generated in an opening of a pattern, or scum is not observed in a bottom portion of the pattern, and resolution is not impaired. On the other hand, in designing the polymer of the present invention, the amount of phenolic hydroxyl groups that can be introduced into 100g of the component (A) in 100g of the component (A) may be about 0.40 mol. In this case, high solubility in the developer of the alkaline aqueous solution can be most expected. However, although a cured film is formed by post-curing after patterning using the photosensitive resin composition of the present invention, a large amount of alkali-soluble phenolic hydroxyl groups may remain in the cured film, and the solubility of the resulting cured film in an alkali chemical may be increased, so that the preferable amount of introduced phenolic hydroxyl groups is adjusted depending on the alkali solubility.

The component (B) in the positive photosensitive resin composition of the present invention is a photosensitizer which generates an acid by light to increase the dissolution rate in an alkaline aqueous solution, and is a compound having a quinonediazide structure. Examples of the component (B) include compounds having a1, 2-naphthoquinone diazidosulfonyl group (1,2-naphthoquinone diazidosulfonyl group) in the molecule.

Examples of the compound having a1, 2-naphthoquinonediazidosulfonyl group in the molecule include compounds having a1, 2-naphthoquinonediazidosulfonyl group represented by the following general formula in the molecule.

[ chemical formula 80]

As the compound capable of introducing the 1, 2-naphthoquinonediazidosulfonyl group, specifically, trihydroxybenzophenone, tetrahydroxybenzophenone, and a novolak resin having: the weight average molecular weight of the novolac resin is in the range of 2,000 to 20,000, preferably 3,000 to 10,000, based on a ballast molecule (バラスト molecule) represented by the following general formula (38') having a phenolic hydroxyl group (hereinafter also referred to as a low nucleus body) or a repeating unit represented by the following formula (43). That is, the resin or compound having a phenolic hydroxyl group exemplified below is preferably one in which the hydrogen atom of the phenolic hydroxyl group is substituted with the above-mentioned 1, 2-naphthoquinonediazidosulfonyl group as the component (B).

[ chemical formula 81]

Wherein R is¹⁰¹～R¹⁰⁶Each independently represents a hydrogen atom, a methyl group, a group represented by the following formula (39), or a group represented by the following formula (40). w is an integer of 0 to 2, z is an integer of 0 to 2, and when z is 0, w is 1 or 2. When z is 0 and w is 1, A ' is a hydrogen atom, a methyl group or a group represented by the following formula (39), when z is 0 and w is 2, one of A ' is a methylene group or a group represented by the following formula (41), the other is a hydrogen atom, a methyl group or a group represented by the following formula (39), and when z is 1, A ' is a methylene group or a group represented by the following formula (41). When z is 2 and w is 1, A 'is methine or a group represented by the following formula (42), and when w is 2, one of A' is methylene or a group represented by the following formula (41), and the other is methine or a group represented by the following formula (42).

[ chemical formula 82]

In the formula, a1, a2, a3, a4, a5, a6 and a7 are integers of 0-3 respectively, a1+ a2 is less than or equal to 5, a3+ a4 is less than or equal to 4, and a6+ a7 is less than or equal to 3.

In this case, the number of benzene rings of the low nucleus bodies (ballast molecules) of the formula (38') is preferably 2 to 20, more preferably 2 to 10, and further preferably 3 to 6, and the ratio of the number of phenolic hydroxyl groups to the number of benzene rings is preferably 0.5 to 2.5, more preferably 0.7 to 2.0, and further preferably 0.8 to 1.5.

Specific examples of such low nuclei (ballast molecules) include the following.

[ chemical formula 83]

[ chemical formula 84]

[ chemical formula 85]

[ chemical formula 86]

[ chemical formula 87]

[ chemical formula 88]

[ chemical formula 89]

Among the low nuclei (ballast molecules) exemplified above, (B-3), (B-29), (B-33), (B-38) and the like are suitably used, and compounds obtained by substituting the hydrogen atom of the phenolic hydroxyl group of these ballast molecules with a1, 2-naphthoquinonediazidosulfonyl group are suitably used as the (B) component of the positive photosensitive resin composition of the present invention.

[ chemical formula 90]

Wherein mm is an integer of 0 to 3.

The novolac resin having the repeating unit represented by the above formula (43) can be synthesized by polycondensing a phenol represented by the following formula (44), specifically, at least one phenol of o-cresol, m-cresol, p-cresol, 3, 5-xylenol and the like, and an aldehyde by a usual method.

[ chemical formula 91]

Wherein mm is an integer of 0 to 3.

In this case, examples of the aldehyde include formaldehyde, para-formaldehyde, acetaldehyde, benzaldehyde, and the like, and formaldehyde is preferable.

The ratio of the phenol represented by the above formula (44) to the aldehyde is preferably 0.2 to 2, particularly preferably 0.3 to 2, in terms of a molar ratio.

As a method for introducing a1, 2-naphthoquinonediazidosulfonyl group into a compound, it is preferable to use a dehydrochlorination condensation reaction of a phenolic hydroxyl group with 1, 2-naphthoquinonediazidosulfonyl chloride using a basic catalyst. Preferably: in the case of the ballast molecule represented by the formula (38'), trihydroxybenzophenone or tetrahydroxybenzophenone, the ratio of substitution of the hydrogen atom of the phenolic hydroxyl group with the 1, 2-naphthoquinonediazidosulfonyl group is 10 to 100 mol%, preferably 50 to 100 mol%; in the case of the novolak resin represented by the above formula (40), the proportion of substitution of the hydrogen atom of the phenolic hydroxyl group with the 1, 2-naphthoquinonediazidosulfonyl group is 2 to 50 mol%, preferably 3 to 27 mol%.

Preferably: the amount of the component (B) added is 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, per 100 parts by mass of the component (A). The component (B) may be used singly or in combination of two or more.

By blending such a component (B), the solubility in an alkaline aqueous solution can be suppressed by the dissolution resistance of the component (B) before exposure, and the system becomes alkaline-insoluble, and the photosensitizer of the component (B) generates an acid by light at the time of exposure, and the dissolution rate in an alkaline aqueous solution increases, and the system becomes alkaline-soluble. That is, when an alkaline aqueous solution is used as the developer, the unexposed portion is insoluble in the developer, and the exposed portion is soluble in the developer, so that a positive pattern can be formed.

The component (C) in the positive photosensitive resin composition of the present invention is a crosslinking agent, which is one or more selected from the group consisting of an amino condensate modified with formaldehyde or formaldehyde-alcohol, 1 phenol compound having an average of 2 or more methylol or alkoxymethyl groups in the molecule, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group, a compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1), and a compound containing 2 or more nitrogen atoms having a glycidyl group represented by the following formula (C-2).

[ chemical formula 92]

Wherein the dotted line represents a bond, Rc represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

Examples of the amino condensate modified with formaldehyde or formaldehyde-alcohol include hexamethoxymethylmelamine, a melamine condensate modified with formaldehyde or formaldehyde-alcohol, and a urea condensate modified with formaldehyde or formaldehyde-alcohol.

The preparation of the above-mentioned melamine condensate modified with formaldehyde or formaldehyde-alcohol is carried out, for example, in the following manner: first, a melamine monomer is modified by methylolation with formalin or by further modification by alkoxylation with an alcohol according to a known method to give a modified melamine represented by the following general formula (45). The alcohol is preferably a lower alcohol, for example, an alcohol having 1 to 4 carbon atoms.

[ chemical formula 93]

In the formula, R₅₀The same or different, and is hydroxymethyl, alkoxymethyl containing alkoxy of 1-4 carbon atoms, or hydrogen atom, wherein at least one is hydroxymethyl or the above alkoxymethyl.

As the above-mentioned R₅₀Examples thereof include an alkoxymethyl group such as a hydroxymethyl group, a methoxymethyl group and an ethoxymethyl group, a hydrogen atom and the like.

Specific examples of the modified melamine represented by the general formula (45) include trimethoxymethyl monohydroxymethyl melamine, dimethoxymethyl monohydroxymethyl melamine, trimethylol melamine, hexamethylol melamine, and hexamethoxy methylol melamine. Subsequently, the modified melamine represented by the above general formula (45) or a polymer thereof (for example, an oligomer such as a dimer or trimer) and formaldehyde are subjected to addition polycondensation to a desired molecular weight by a conventional method to obtain a melamine condensate modified with formaldehyde or formaldehyde-alcohol.

Further, the above-mentioned urea condensate modified with formaldehyde or formaldehyde-alcohol is prepared, for example, in the following manner: the urea condensate of the desired molecular weight is modified by methylolation with formaldehyde or further by alkoxylation with an alcohol according to known methods.

Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensate, ethoxymethylated urea condensate, and propoxymethylated urea condensate.

One or more of these modified melamine condensates and modified urea condensates may be used in combination.

Examples of the phenol compound having an average of 2 or more hydroxymethyl groups or alkoxymethyl groups in one molecule include (2-hydroxy-5-methyl) -1, 3-benzenedimethanol, 2 ', 6, 6' -tetramethoxymethyl bisphenol A, and compounds represented by the following formulae (C-3) to (C-7).

[ chemical formula 94]

The crosslinking agent may be used singly or in combination of two or more.

Examples of the compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a glycidyl group include compounds obtained by reacting a hydroxyl group of bisphenol a, tris (4-hydroxyphenyl) methane, or 1,1, 1-tris (4-hydroxyphenyl) ethane with epichlorohydrin in the presence of a base. Suitable examples of the compound having a glycidyl group as a hydrogen atom of a hydroxyl group of a polyhydric phenol include compounds represented by the following formulas (C-8) to (C-14).

[ chemical formula 95]

Wherein t is more than or equal to 2 and less than or equal to 3.

One or both of these compounds in which the hydroxyl group of the polyhydric phenol is substituted with a glycidyl ether oxy group can be used as the crosslinking agent.

Examples of the compound in which a hydrogen atom of a hydroxyl group of a polyhydric phenol is substituted with a substituent represented by the following formula (C-1) include compounds represented by the following formula (C-15) containing 2 or more of the substituents.

[ chemical formula 96]

In the formula, the dotted line represents a bond.

[ chemical formula 97]

Wherein u is more than or equal to 1 and less than or equal to 3.

Further, examples of the compound containing 2 or more glycidyl group-containing nitrogen atoms represented by the following formula (C-2) include compounds represented by the following formula (C-16).

[ chemical formula 98]

Wherein the dotted line represents a bond, Rc represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and s represents 1 or 2.

[ chemical formula 99]

Wherein W represents a linear, branched, or cyclic alkylene group having 2 to 12 carbon atoms or a divalent aromatic group.

Examples of the compound represented by the above formula (C-16) include compounds represented by the following formulas (C-17) to (C-20).

[ chemical formula 100]

Further, as the compound containing 2 or more glycidyl group-having nitrogen atoms represented by the above formula (C-2), a compound represented by the following formula (C-21) can be suitably used.

[ chemical formula 101]

One or two of these compounds containing 2 or more glycidyl group-having nitrogen atoms represented by the above formula (C-2) can be used as a crosslinking agent.

(C) The component (b) is a component which causes a crosslinking reaction in post-curing after the patterning of the positive photosensitive resin composition using the polymer of the present invention, and further improves the strength of the cured product. The weight average molecular weight of the component (C) is preferably 150 to 10,000, particularly preferably 200 to 3,000, from the viewpoint of curability and heat resistance.

The component (D) in the positive photosensitive resin composition is a solvent. (D) The solvent for component (B) is not limited as long as it dissolves component (a) and component (B). Examples of the solvent include ketones such as cyclohexanone, cyclopentanone, and methyl-2-n-pentanone; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butyl propionate, propylene glycol mono-t-butyl ether acetate, and γ -butyrolactone, and one or more of these solvents can be used. Particularly preferred is ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ -butyrolactone, or a mixed solvent thereof.

The amount of the component (D) is preferably 50 to 2,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B).

The positive photosensitive resin composition of the present invention may further contain (E) a compound that generates an acid or a radical by heat. In the step of heating at 100 to 300 ℃ and post-curing, which is performed after the pattern formation, the component (E), i.e., the compound that generates an acid or a radical by heat, may be added for the purpose of promoting the crosslinking reaction with the component (a) by heat.

In particular, it is preferable that the component (E) does not promote the curing of the film until the pattern is formed by development, and does not inhibit the pattern formation. In order to achieve the object, it is preferable that the component (E) does not generate an acid or a radical at a temperature in the step of removing the solvent and drying after coating the photosensitive resin composition, and generates an acid or a radical by heat treatment after pattern formation, thereby promoting curing of the pattern or the coating film of the positive photosensitive resin composition. Specifically, the following compounds are preferred: a compound which decomposes and generates an acid or a radical by a heat treatment at 100 to 300 ℃, preferably 150 to 300 ℃. By containing such a component (E), in the step of heating at 100 to 300 ℃ and post-curing performed after the pattern formation, the pattern or coating of the positive photosensitive resin composition can be changed into a pattern or coating in which the crosslinking and curing reaction has further progressed. (E) The component (c) can further improve the mechanical strength, chemical resistance, adhesion, and the like of the obtained pattern or coating film by further performing crosslinking and curing reaction.

As the compound which generates an acid by suitable heat, the compounds described in paragraphs 0061 to 0085 of Japanese patent application laid-open No. 2007-199653 can be used.

The amount of the compound generating an acid by heat is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 30 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the (a) component in the positive photosensitive resin composition of the present invention.

Examples of the compound which generates a radical by suitable heat include organic peroxides such as diisopropylbenzene hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-butyl hydroperoxide and tert-butyltrimethylsilyl peroxide (tert-butyltrimethylsilyl peroxide), and radical initiators composed of only carbon and hydrogen such as 2, 3-dimethyl-2, 3-diphenylbutane. Among these, a radical initiator composed of only carbon and hydrogen is more preferable because it has a large activation energy and is less likely to be decomposed by heat during drying.

The amount of the compound generating radicals by heat is preferably 0.5 to 4 parts by mass, and more preferably 1 to 3 parts by mass, based on 100 parts by mass of the component (a) in the positive photosensitive resin composition of the present invention.

The positive photosensitive resin composition of the present invention may further contain a component (F) other than the components (a), (B), (C), (D) and (E). Examples of the component (F) include adhesion promoters and surfactants, and the following compounds can be suitably used as the surfactant.

The surfactant is preferably a nonionic surfactant, and examples thereof include fluorine-based surfactants, specifically perfluoroalkyl alcohol polyoxyethylene ether, fluorinated alkyl esters, perfluoroalkyl amine oxides, fluorine-containing organosilicone compounds, and the like.

As these surfactants, commercially available surfactants can be used, and examples thereof include Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited Inc.), Surflon "S-141" and "S-145" (manufactured by AGC Inc., above), Unidyne "DS-401", "DS-4031" and "DS-451" (manufactured by DAIKIN INDUSTRIES, LTD.), Megafac "F-8151" (manufactured by CORDIC CORPORATION), and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.). Among them, Fluorad "FC-4430" (manufactured by Sumitomo 3M Limited Inc.) and "X-70-093" (manufactured by Shin-Etsu Chemical Co., Ltd.) are preferable.

(Pattern Forming method)

Hereinafter, a method for forming a pattern using the positive photosensitive resin composition of the present invention will be described.

In the positive photosensitive resin composition of the present invention, the patterning may be performed by including the steps of: (1) a step of coating the positive photosensitive resin composition of the present invention on a substrate to form a photosensitive material coating film; (2) then, after the heating treatment, exposing the photosensitive material coating film with a high-energy ray or electron beam having a wavelength of 190-500 nm through a photomask; (3) and a step of developing the substrate with a developer of an alkaline aqueous solution. Specifically, the coating can be performed on a silicon wafer or SiO by a known lithography technique, for example, a spin coating method (spin coating method)₂A substrate, a SiN substrate, or a substrate having a pattern such as copper wiring formed thereon is coated with a photosensitive resin composition, and prebaked at 80 to 130 ℃ for about 50 to 600 seconds to form a photosensitive material coating film having a thickness of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.

In the spin coating method, a photosensitive resin composition is applied to a substrate by dispensing about 5mL of the photosensitive resin composition onto a silicon substrate and then rotating the substrate. At this time, the film thickness of the photosensitive material coating film on the substrate can be easily adjusted by adjusting the rotation speed.

Then, a mask for forming a target pattern is masked on the photosensitive material coating film so that the exposure amount is 1 to 5,000mJ/cm²About, preferably 100 to 2,000mJ/cm²High-energy rays or electron beams having a wavelength of 190 to 500nm, such as i-rays and g-rays, are irradiated in a left-right manner.

Then, development is performed. In the positive photosensitive resin composition of the present invention, development can be performed using an alkaline aqueous solution.

A suitable aqueous alkaline solution that can be used for alkaline development is a 2.38% solution of tetramethylammonium hydroxide (TMAH). The development can be carried out by a usual method such as a spray method or a paddle development method, or by immersion in a developer. Then, if necessary, cleaning, rinsing, drying, etc. are performed to obtain a resist film having a desired pattern.

The cured coating can be formed by heating and post-curing the patterned coating obtained by the above-described pattern forming method at a temperature of 100 to 300 ℃, preferably 150 to 300 ℃, and more preferably 180 to 250 ℃ using an oven or a hot plate. In the post-curing step, when the post-curing temperature is 100 to 300 ℃, the crosslinking density of the coating film of the photosensitive resin composition can be increased and the residual volatile components can be removed, and the post-curing step is preferable from the viewpoint of adhesion to a substrate, heat resistance, strength, and electrical characteristics. The post-curing time may be set to 10 minutes to 10 hours.

(Dry film Forming and Pattern Forming method)

Further, a photosensitive dry film having a structure in which a photosensitive resin layer having a thickness of 5 to 100 μm is sandwiched between a support film and a protective film can be produced by the following steps using a positive photosensitive resin composition using the polymer of the present invention.

(i) A step of forming a photosensitive resin layer by continuously applying a positive photosensitive resin composition using the polymer of the present invention on a support film;

(ii) a step of continuously drying the photosensitive resin layer;

(iii) and a step of bonding a protective film to the photosensitive resin layer.

Through the above process, a photosensitive dry film can be manufactured.

Further, as a pattern forming method using the dry film, a pattern can be formed through the following steps:

(i) a step of closely adhering the photosensitive resin layer exposed by peeling the protective film from the photosensitive dry film to the substrate;

(ii) exposing the photosensitive resin layer with a high-energy ray or an electron beam having a wavelength of 190 to 500nm through the support film or through a photomask in a state where the support film is peeled;

(iii) and a step of developing with a developer.

Further, (iv) a step of post-curing the coating film patterned by development at the same temperature of 100 to 300 ℃ as described above, whereby a cured film having improved adhesion to a substrate, heat resistance, strength, and electrical characteristics can be obtained.

(protective coating film for covering wiring, circuit, substrate, etc.)

The pattern and the protective film formed as described above are used for the purpose of covering a protective film for a wiring, a circuit, a substrate, or the like, have excellent insulating properties, exhibit excellent adhesion to a metal layer such as Cu of the covered wiring or circuit, a metal electrode on the substrate, or an insulating substrate such as SiN present on the covered wiring or circuit, have appropriate mechanical strength as the protective film, and can greatly improve resolution performance for enabling fine pattern formation.

The cured film obtained in this manner is excellent in adhesion to a substrate, heat resistance, electrical characteristics, mechanical strength, and chemical resistance to an alkaline peeling solution and the like, and is also excellent in reliability of a semiconductor element as a protective film, and particularly can prevent the occurrence of cracks in a temperature cycle test, and is suitable for use as a protective film for an electric or electronic component, a semiconductor element, and the like.

The protective film is effective for use as an insulating film for a semiconductor element including a rewiring application, an insulating film for a multilayer printed board, a solder mask, a coverlay film, and the like, from the viewpoint of heat resistance, chemical resistance, and insulation properties.