Polyamic acid ester and resin composition

Abstract

A polyamic acid ester comprising a structural unit (A) derived from a tetracarboxylic acid dianhydride and a structural unit (B) derived from a diamine compound, wherein at least a part of the structural unit (A) has an unsaturated double bond, and the 380 nm light transmittance of the polyamic acid ester is at least 10% in a 3-methoxy-N,N-dimethylpropanamide solution having a solid content concentration of 0.1 mass %.

Description

Polyamic acid ester and resin composition

[0001] The present disclosure relates to a polyamic acid ester and a resin composition.

[0002] In recent years, organic materials with high heat resistance, such as polyimide resins, have been widely used as protective film materials for semiconductor integrated circuits (LSIs) (see, for example, Patent Document 1). Such protective films (cured films) using polyimide resins are obtained by applying a polyimide precursor or a resin composition containing the polyimide precursor to a substrate, drying the applied resin film, and then heating the resin film to cure it.

[0003] Japanese Patent Application Laid-Open No. 2016-199662

[0004] With the miniaturization of semiconductor integrated circuits, resin compositions are required to be capable of forming excellent pattern shapes. For example, polyimide precursors such as polyamic acid esters are desirable because they can produce patterned cured films having highly accurate pattern shapes corresponding to pattern exposure.

[0005] The present disclosure has been made in view of the above-described conventional circumstances, and an object of the present disclosure is to provide a polyamic acid ester that can be used to produce a patterned cured film having a highly accurate pattern shape, and a resin composition containing the same.

[0006] Specific means for achieving the above object are as follows. <1> A polyamic acid ester comprising a structural unit (A) derived from a tetracarboxylic dianhydride and a structural unit (B) derived from a diamine compound, wherein at least a portion of the structural unit (A) has an unsaturated double bond, and wherein the polyamic acid ester has a light transmittance of 10% or more at 380 nm when dissolved in 3-methoxy-N,N-dimethylpropanamide at a solids concentration of 0.1% by mass. <2> The polyamic acid ester according to <1>, wherein the structural unit (A) comprises a structural unit (A1-1) in which two acid anhydride groups contained in the tetracarboxylic dianhydride are not bonded to aromatic rings. <3> The polyamic acid ester according to <1>, wherein the structural unit (A) does not comprise an aromatic ring or comprises a structural unit (A1-2) in which the ratio of the number of aromatic rings contained in the tetracarboxylic dianhydride to the molecular weight of the tetracarboxylic dianhydride is less than 0.0068. <4> The polyamic acid ester according to <2>, wherein the content of the structural unit (A1-1) in the structural unit (A) is 25 mol % or more relative to the structural unit (A). <5> The polyamic acid ester according to <3>, wherein the content of the structural unit (A1-2) in the structural unit (A) is 25 mol % or more relative to the structural unit (A). <6> The polyamic acid ester according to any one of <1> to <5>, wherein the tetracarboxylic dianhydride includes at least one of compounds represented by the following chemical formulas (A-1) to (A-6):

[0007] <7> The polyamic acid ester according to any one of <1> to <6>, wherein the structural unit (A) includes a structural unit (A2) in which two acid anhydride groups contained in the tetracarboxylic dianhydride are bonded to an aromatic ring. <8> The polyamic acid ester according to any one of <1> to <7>, which is a compound having a structural unit represented by the following general formula (6):

[0008]

[0009] (In general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ６ and R ７ is a group represented by the following general formula (7), and the tetravalent organic group represented by X does not contain an aromatic ring, or if it contains an aromatic ring, the aromatic ring is not bonded to four carbonyl groups.

[0010]

[0011] (In general formula (7), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10. <9> The polyamic acid ester according to any one of <1> to <8>, which has a weight-average molecular weight of 20,000 or more. <10> The polyamic acid ester according to any one of <1> to <9>, which has a light transmittance at 400 nm of 70% or more when dissolved in 3-methoxy-N,N-dimethylpropanamide at a solids concentration of 0.1% by mass. <11> A resin composition comprising the polyamic acid ester according to any one of <1> to <10>.

[0012] According to the present disclosure, it is possible to provide a polyamic acid ester and a resin composition containing the same that can produce a patterned cured film having a highly accurate pattern shape.

[0013] 1 is a graph showing the light transmittance of solutions using polyamic acid esters 4, 10, and 12 to 14. 2 is a graph showing the light transmittance of solutions using polyamic acid esters 2, 4, 10, and 12.

[0014] Hereinafter, embodiments for carrying out the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0015] In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in the present disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another staged numerical range. Furthermore, in numerical ranges described in the present disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the Examples. In the present disclosure, each component may contain multiple corresponding substances. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the terms "layer" and "film" include cases where the layer or film is formed over the entire area when the area where the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area.

[0016] <Polyamic Acid Ester> The polyamic acid ester of the present disclosure comprises a structural unit (A) derived from a tetracarboxylic dianhydride and a structural unit (B) derived from a diamine compound, wherein at least a portion of the structural unit (A) has an unsaturated double bond, and when made into a 3-methoxy-N,N-dimethylpropanamide solution having a solids concentration of 0.1 mass %, the polyamic acid ester has a light transmittance of 10% or more at 380 nm.

[0017] The polyamic acid ester of the present disclosure has excellent light transmittance, as evidenced by its 380 nm light transmittance of 10% or more when dissolved in a 3-methoxy-N,N-dimethylpropanamide solution having a solids concentration of 0.1% by mass. Therefore, excellent pattern shapes can be formed by using a resin composition containing the polyamic acid ester. While the reasons for this are unclear, they are presumed to be as follows. First, if the light transmittance is less than 10%, when a photosensitive film containing the polyamic acid ester applied to a substrate or the like is subjected to pattern exposure, it becomes difficult for light to reach the bottom of the photosensitive film. This makes it difficult to obtain a patterned cured film having a highly accurate pattern shape corresponding to the pattern exposure. For example, in the case of a negative photosensitive film, the resulting patterned cured film is likely to have an inverse tapered shape, while in the case of a positive photosensitive film, the resulting patterned cured film is likely to have a tapered shape. On the other hand, the polyamic acid ester and the resin composition containing the polyamic acid ester according to the present disclosure have excellent light transmittance, and therefore, when a photosensitive film containing the polyamic acid ester coated on a substrate or the like is subjected to pattern exposure, light is irradiated all the way to the bottom of the photosensitive film, thereby obtaining a patterned cured film having a highly accurate pattern shape corresponding to the pattern exposure.

[0018] The polyamic acid ester of the present disclosure may be used in materials requiring photosensitivity (for example, negative or positive photosensitive resin compositions, preferably negative photosensitive resin compositions), or in materials not requiring photosensitivity. The polyamic acid ester of the present disclosure has an unsaturated double bond, and is therefore preferably used in materials requiring photosensitivity.

[0019] The polyamic acid ester of the present disclosure may have a light transmittance at 380 nm of 20% or more, 25% or more, or 50% or more when prepared as a 3-methoxy-N,N-dimethylpropanamide solution having a solids concentration of 0.1% by mass. The upper limit of the light transmittance at 380 nm is not particularly limited as long as it is 100%.

[0020] The light transmittance can be measured, for example, as follows: A polyamic acid ester powder is dissolved in 3-methoxy-N,N-dimethylpropanamide to a concentration of 0.1% by mass, and the solution is placed in a measurement cell. The light transmittance at a specific wavelength (for example, a wavelength in the range of 300 nm to 500 nm) is then measured using a spectrophotometer (for example, U-3900H manufactured by Hitachi High-Tech Science Corporation).

[0021] The polyamic acid ester according to the present disclosure may have a light transmittance at 400 nm of 30% or more, 40% or more, 70% or more, 75% or more, or 80% or more when it is prepared as a 3-methoxy-N,N-dimethylpropanamide solution having a solids concentration of 0.1% by mass. The upper limit of the light transmittance at 400 nm is not particularly limited as long as it is 100%.

[0022] The light transmittance can be appropriately adjusted by, for example, changing the tetracarboxylic dianhydride and the diamine compound. Specifically, the light transmittance value tends to be increased by methods such as reducing the amount of the structural unit (A) derived from the tetracarboxylic dianhydride containing an aromatic ring, reducing the proportion of aromatic rings in all the structural units (A), reducing the amount of the structural unit (B) derived from the diamine compound containing an aromatic ring, or reducing the proportion of aromatic rings in all the structural units (B).

[0023] The polyamic acid ester of the present disclosure is not particularly limited as long as it contains the structural unit (A) and the structural unit (B), at least a portion of which has an unsaturated double bond, and is a compound having the above-mentioned light transmittance at 380 nm of 10% or more. Possible forms of the polyamic acid ester are described below.

[0024] Examples of tetracarboxylic dianhydrides include compounds containing two acid anhydride groups, the two acid anhydride groups being linked by a single bond, a linking group, or a composite linking group that combines two or more linking groups. Examples of the linking group include an alkylene group, a halogenated alkylene group, a phenylene group (however, not bonded to an acid anhydride group), a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(RＡ ) ２ -;R Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;R Ｂ each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more.

[0025] From the viewpoint of durability when formed into a cured product, the structural unit (A) preferably contains an alicyclic structure. The structural unit (A) may contain one alicyclic structure or two or more alicyclic structures. When containing two or more alicyclic structures, two alicyclic rings may be bonded at two positions by at least one of a single bond and a linking group to form a five- or six-membered ring containing a linking group between the two alicyclic rings. The alicyclic ring may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.

[0026] Examples of the alicyclic structure include a tricyclodecane skeleton, a cyclohexane skeleton, a cyclopentane skeleton, a cyclobutene skeleton, a 1,3-adamantane skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, a hydrogenated bisphenol S skeleton, and an isobornyl skeleton.

[0027] The structural unit (A) may or may not contain an aromatic ring. When the structural unit (A) contains an aromatic ring, the number of aromatic rings is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0028] When the structural unit (A) contains two or more aromatic rings, the aromatic rings may be linked by a single bond, or may be linked by a linking group, a composite linking group that combines two or more types of linking groups, or the like. Examples of the linking group include an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -;R Ａeach independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) 2-O-) ｎ ;R Ｂ each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or greater.) In addition, two benzene rings may be bonded at two positions by at least one of a single bond and a linking group to form a five- or six-membered ring containing a linking group between the two aromatic rings.

[0029] When the structural unit (A) contains an aromatic ring, examples of the aromatic ring include a benzene ring, a naphthalene ring, and a phenanthrene ring. Among these, a benzene ring is preferred from the viewpoint of improving the light transmittance of the polyamic acid ester in the ultraviolet region. When the structural unit (A) contains an aromatic ring, each aromatic ring may have a substituent or may be unsubstituted. Examples of the substituent on the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.

[0030] The polyamic acid ester of the present disclosure may contain one type of structural unit (A), or may contain two or more types of structural units (A). When two or more types of structural units (A) are contained, the polyamic acid ester of the present disclosure may contain a structural unit containing an alicyclic structure and a structural unit containing an aromatic ring, or may contain a structural unit not containing an alicyclic structure or an aromatic ring, and a structural unit containing an aromatic ring.

[0031] At least a portion of the structural units (A) contained in the polyamic acid ester of the present disclosure preferably have an unsaturated double bond and satisfy the following (1) or (2): (1) The structural unit (A) contains a structural unit (A1-1) in which the two acid anhydride groups contained in the tetracarboxylic acid dianhydride are not bonded to aromatic rings; (2) The structural unit (A) contains a structural unit (A1-2) in which the ratio of the number of aromatic rings contained in the tetracarboxylic acid dianhydride to the molecular weight of the tetracarboxylic acid dianhydride is less than 0.0068.

[0032] The structural unit (A1-1) may contain an aromatic ring that is not bonded to an acid anhydride group, as long as the two acid anhydride groups are not bonded to an aromatic ring. Even when the structural unit (A1-1) contains an aromatic ring, the aromatic ring is not bonded to the two acid anhydride groups, and instead, another functional group, another structure, etc. is bonded to the two acid anhydride groups. This is presumably to reduce the proportion of aromatic rings in the structural unit (A1-1), which tends to improve the light transmittance of the polyamic acid ester and resin compositions containing it. From the perspective of the light transmittance of the polyamic acid ester and resin compositions containing it, it is preferable that the structural unit (A1-1) does not contain an aromatic ring that is not bonded to the two acid anhydride groups.

[0033] From the viewpoint of durability when formed into a cured product, the structural unit (A1-1) preferably contains the above-mentioned alicyclic structure. The structural unit (A1-1) may contain one alicyclic structure, or two or more alicyclic structures.

[0034] The structural unit (A1-2) may be any unit as long as it does not contain any aromatic rings, or the ratio of the number of aromatic rings contained in the tetracarboxylic dianhydride to the molecular weight of the tetracarboxylic dianhydride is less than 0.0068. Hereinafter, the ratio of the number of aromatic rings contained in the tetracarboxylic dianhydride to the molecular weight of the tetracarboxylic dianhydride is also referred to as the "aromatic ring content 1."

[0035] In the structural unit (A1-2), the aromatic ring content 1 may be 0.0060 or less, 0.0050 or less, or 0.0040 or less, or it may be 0, in other words, the structural unit may not contain any aromatic rings.

[0036] The tetracarboxylic dianhydride preferably includes at least one of the compounds represented by the following chemical formulas (A-1) to (A-6). The compounds represented by the following chemical formulas (A-1) to (A-6) are preferred examples of the tetracarboxylic dianhydride that constitutes the structural unit (A1-1) and the tetracarboxylic dianhydride that constitutes the structural unit (A1-2).

[0037]

[0038] The compounds represented by chemical formula (A-1) and (A-5) are tetracarboxylic dianhydrides containing an aromatic ring that is not bonded to two acid anhydride groups. The compounds represented by chemical formulas (A-2) to (A-4) and (A-6) are tetracarboxylic dianhydrides that do not contain an aromatic ring.

[0039] The tetracarboxylic acid dianhydride preferably contains at least one of the compounds represented by the chemical formula (A-2), the compounds represented by the chemical formula (A-4), and the compounds represented by the chemical formula (A-6). By using a polyamic acid ester containing a structural unit derived from such a compound, a cured product with low stress can be easily obtained.

[0040] The structural unit (A) may include a structural unit (A2) in which two acid anhydride groups contained in a tetracarboxylic dianhydride are bonded to an aromatic ring. By including the structural unit (A2), the durability of the cured product is improved.

[0041] In the structural unit (A2), the aromatic ring content 1 may be 0.0045 or more, 0.0050 or more, or 0.0060 or more. The upper limit may be, for example, 0.0100, 0.0080, or 0.0070.

[0042] The structural unit (A2) may contain a group represented by the following general formulae (A) to (E).

[0043]

[0044] In the general formula (D), A and B each independently represent a single bond, a methylene group, a halogenated methylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), or a silylene bond (—Si(R Ａ ) ２ -;R Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and A and B cannot both be single bonds.

[0045] In the general formula (E), C represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -;R Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;R Ｂ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group comprising at least two of these. C may also be a structure represented by the following formula (C1):

[0046]

[0047] The alkylene group represented by C in general formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. Specific examples of the alkylene group represented by C in general formula (E) include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethyl ...2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-ethyltrimethylene group, a 2-methyltetramethylene group, a 2-methyltetram branched alkylene groups such as ethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-methylpentamethylene, 2-methylpentamethylene, 3-methylpentamethylene, 1-ethyltetramethylene, 2-ethyltetramethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2,3-dimethyltetramethylene, and 1,4-dimethyltetramethylene; and the like. Among these, a methylene group is preferred.

[0048] The halogenated alkylene group represented by C in general formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms. Specific examples of the halogenated alkylene group represented by C in general formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in the above-mentioned general formula (E) has been substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.

[0049] R contained in the silylene bond or siloxane bond Ａ or RＢ The alkyl group represented by R is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Ａ or R Ｂ Specific examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.

[0050] The combination of A and B in general formula (D) is not particularly limited, and preferred are a combination of a methylene group and an ether bond, a combination of a methylene group and a sulfide bond, a combination of a carbonyl group and an ether bond, etc. Preferred as C in general formula (E) are a single bond, an ether bond, a carbonyl group, etc.

[0051] Examples of the tetracarboxylic dianhydride of the structural unit (A2) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. terylenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis( 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexa Examples include fluoro-2,2-bis{4'-(2,3-dicarboxyphenoxy)phenyl}propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis{4'-(3,4-dicarboxyphenoxy)phenyl}propane dianhydride, 4,4'-oxydiphthalic dianhydride, 4,4'-sulfonyldiphthalic dianhydride, and 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride.

[0052] When the structural unit (A) contains the structural unit (A1-1) or the structural unit (A1-2), the content of the structural unit (A1-1) in the structural unit (A) and the content of the structural unit (A1-2) in the structural unit (A) are each independently preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more. There are no particular upper limits to these proportions, and they may be 100 mol%, 80 mol% or less, or 60 mol% or less.

[0053] At least a portion of the structural unit (A) has an unsaturated double bond. The unsaturated double bond contained in the structural unit (A) may be present in the ester portion of the tetracarboxylic dianhydride. In this case, R of the -COOR group has an unsaturated double bond. It is preferable that R contains a group represented by the following general formula (7):

[0054]

[0055] In general formula (7), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0056] R in general formula (7) ８ ~R １０ The aliphatic hydrocarbon group represented by R has 1 to 3 carbon atoms, preferably 1 or 2. ８ ~R １０ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., with a methyl group being preferred.

[0057] R in general formula (7) ８ ~R １０ As a combination of ８ and R ９ is a hydrogen atom, and R １０ is preferably a hydrogen atom or a methyl group.

[0058] In general formula (7), q is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3.

[0059] The polyamic acid ester contains a structural unit (B) derived from a diamine compound. The structural unit (B) is not particularly limited as long as it contains a structure derived from a diamine compound, and may or may not contain an aromatic ring. From the viewpoint of durability when formed into a cured product, it is preferable that the structural unit (B) contains an aromatic ring.

[0060] The structural unit (B) preferably contains a structural unit represented by -NH-Y-NH-. Y is a divalent organic group. The divalent organic group represented by Y preferably has 6 to 25 carbon atoms, more preferably 6 to 14 carbon atoms, and even more preferably 12 to 14 carbon atoms. The divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoints of heat resistance and high elasticity, the divalent organic group represented by Y is preferably a divalent aromatic group.

[0061] Specific examples of the divalent aromatic group represented by Y include groups represented by the following general formula (F) and the following general formula (G).

[0062]

[0063] In general formula (F) or general formula (G), R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, or a phenyl group, and n each independently represents an integer of 0 to 4. In general formula (G), D represents a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a silylene bond (—Si(R Ａ ) ２ -;R Ａ each independently represents a hydrogen atom, an alkyl group, or a phenyl group; a siloxane bond (—O—(Si(R Ｂ ) ２ -O-) ｎ ;R Ｂ each independently represents a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more. ) or a divalent group combining at least two of them. D may also be a structure represented by the above formula (C1). Specific examples of D in general formula (G) are the same as the specific examples of C in general formula (E). D in general formula (G) is preferably a single bond.

[0064] The alkyl group represented by R in general formula (F) or (G) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms. Specific examples of the alkyl group represented by R in general formula (F) or (G) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, and the like.

[0065] The alkoxy group represented by R in general formula (F) or (G) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms. Specific examples of the alkoxy group represented by R in general formula (F) or (G) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.

[0066] The halogenated alkyl group represented by R in general formula (F) or general formula (G) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms. Specific examples of the halogenated alkyl group represented by R in general formula (F) or general formula (G) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in general formula (F) or general formula (G) is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.

[0067] In formula (F) or formula (G), n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0068] Specific examples of the divalent aliphatic group represented by Y include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure.

[0069] The linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms. Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.

[0070] The cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms. Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.

[0071] The unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms. Of these, the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene oxide structure. The alkylene group in the alkylene oxide structure may be linear or branched. The unit structure in the polyalkylene oxide structure may be of one type or two or more types.

[0072] Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which the silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-octyl, 2-ethylhexyl, and n-dodecyl. Among these, methyl is preferred. The aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted. Specific examples of the substituent in the aryl group when it has a substituent include a halogen atom, an alkoxy group, and a hydroxy group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Among these, phenyl is preferred. The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one type or of two or more types. The silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (6) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.

[0073] Examples of the diamine compound of the structural unit (B) include 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4 ... , 2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4'-diaminodiphenyl sulfone, 2,2'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 2,4'-diaminodiphenyl sulfide, 2,2'-diaminodiphenyl sulfide, o-tolidine, o-tolidine sulfone, 4,4'-methylenebis(2,6-diene) 4,4'-methylenebis(2,6-diisopropylaniline), 2,4-diaminomesitylene, 1,5-diaminonaphthalene, 4,4'-benzophenonediamine, bis-{4-(4'-aminophenoxy)phenyl}sulfone, 2,2-bis{4-(4'-aminophenoxy)phenyl}propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis{4-(3'-aminophenoxy)phenyl}sulfone, 2,2-bis(4-aminophen (aminophenyl)propane, 9,9-bis(4-aminophenyl)fluorene, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 1,Examples of the diamine compounds include 4-cyclohexanediamine, 1,3-cyclohexanediamine, and diaminopolysiloxane. The diamine compounds may be used alone or in combination of two or more.

[0074] The polyamic acid ester having an unsaturated double bond may be, for example, a polyamic acid ester having a constitutional unit represented by the following general formula (6).

[0075]

[0076] In general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７ are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ６ and R ７ is a group represented by the following general formula (7), and the tetravalent organic group represented by X does not contain an aromatic ring, or if it contains an aromatic ring, the aromatic ring is not bonded to four carbonyl groups.

[0077]

[0078] In general formula (7), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; and q represents an integer of 1 to 10.

[0079] R in general formula (6) ６ and R ７ The carbon number of the aliphatic hydrocarbon group represented by R is 1 to 4, and preferably 1 or 2. ６ and R ７ Specific examples of the aliphatic hydrocarbon group represented by the formula include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

[0080] In general formula (6), R ６ and R ７ At least one of the groups represented by the general formula (7) is R ６ and R ７ and more preferably, both of these are groups represented by the general formula (7).

[0081] General formula (7) has the same meaning as general formula (7) described for structural unit (A). Y in general formula (6) has the same meaning as Y described for structural unit (B). Examples of X in general formula (6) include the linking groups and composite linking groups described for structural units (A1-1) and (A1-2).

[0082] In general formula (6), the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 4 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0083] The tetravalent organic group represented by X may contain an aromatic ring. When X contains an aromatic ring, the aromatic ring is not bonded to four carbonyl groups.

[0084] In general formula (6), specific examples of X include the groups shown below, but the present disclosure is not limited to the specific examples below.

[0085]

[0086] When X corresponds to a residue derived from a tetracarboxylic acid dianhydride, specific examples of the tetracarboxylic acid dianhydride that is the source of the residue include the tetracarboxylic acid dianhydrides exemplified for the structural units (A1-1) and (A1-2).

[0087] In the general formula (6), -COOR ６ The —COOR group and the —CONH— group are in the ortho position relative to each other. ７ The group and the —CO— group are preferably in the ortho position relative to each other.

[0088] The polyamic acid ester having an unsaturated double bond may further have a constituent unit represented by the following general formula (6-1) in addition to the constituent unit represented by the general formula (6).

[0089]

[0090] In general formula (6-1), X １ represents a tetravalent organic group, and Y represents a divalent organic group. ６ and R ７are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ６ and R ７ At least one of the following is a group represented by the following general formula (7), and X １ The tetravalent organic group represented by the formula (6-1) contains an aromatic ring. １ The two carbonyl groups in the general formula (6-1) are preferably bonded to an aromatic ring contained in X １ The remaining two carbonyl groups are bonded to one aromatic ring (first aromatic ring) contained in X １ It is more preferable that the aromatic ring is bonded to another aromatic ring (second aromatic ring) contained in the above.

[0091] Y and R in general formula (6-1) ６ , R ７ represents Y and R in general formula (6). ６ , R ７ are synonymous with each other.

[0092] X in general formula (6-1) １ Specific examples of the structural unit (A2) include the general formulae (A) to (E) described above.

[0093] When X corresponds to a residue derived from a tetracarboxylic acid dianhydride, specific examples of the tetracarboxylic acid dianhydride that is the source of the residue include the tetracarboxylic acid dianhydrides explained in connection with the structural unit (A2).

[0094] The polyamic acid ester may have other structural units in addition to the general formula (6) and the general formula (6-1). The other structural units include R ６ and R ７ and wherein none of the above is a group represented by general formula (7).

[0095] The content of the structural unit represented by general formula (6) in the polyamic acid ester is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total structural units contained in the polyamic acid ester. There is no particular upper limit to this percentage, and it may be 100 mol%, 80 mol% or less, or 60 mol% or less.

[0096] The total content of the structural units represented by general formula (6) and the structural units represented by general formula (6-1) in the polyamic acid ester is preferably 50 mol% or more, more preferably 80 mol% or more and 100 mol% or less, and even more preferably 90 mol% or more and 100 mol% or less, based on all structural units contained in the polyamic acid ester.

[0097] The polyamic acid ester may be synthesized using a tetracarboxylic dianhydride and a diamine compound. In this case, X corresponds to a residue derived from the tetracarboxylic dianhydride, and Y corresponds to a residue derived from the diamine compound. The polyamic acid ester may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.

[0098]

[0099] In the general formula (8), X is the same as X in the general formula (6), and specific examples and preferred examples are also the same.

[0100] Polyamic acid esters can be prepared, for example, by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R—OH in an organic solvent such as N-methyl-2-pyrrolidone to form a diester derivative, and then by reacting the diester derivative with H ２ N-Y-NH ２ or a condensation reaction of a tetracarboxylic acid dianhydride with a diamine compound represented by the formula: ２ N-Y-NH ２In an organic solvent, a diamine compound represented by the formula (I) is reacted with a polyamic acid to obtain a polyamic acid, and a compound represented by R—OH is added thereto, and the resulting mixture is reacted in an organic solvent to introduce an ester group. ２ N-Y-NH ２ Y in the diamine compound represented by formula (6) is the same as Y in formula (6), and specific examples and preferred examples are also the same. Furthermore, R in the compound represented by R-OH represents a group represented by formula (7) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and specific examples and preferred examples are the same as R in formula (6). ６ and R ７ This is the same as in the case of

[0101] Tetracarboxylic acid dianhydride represented by formula (8), H ２ N-Y-NH ２ The diamine compound represented by the formula (8) and the compound represented by R—OH may each be used alone or in combination of two or more. The polyamic acid ester can be prepared by reacting a tetracarboxylic dianhydride represented by the formula (8) below with a compound represented by R—OH to form a diester derivative, which is then converted into an acid chloride by reacting with a chlorinating agent such as thionyl chloride, and then reacting with a chlorinating agent such as thionyl chloride to form an acid chloride. ２ N-Y-NH ２ Furthermore, polyamic acid esters can be obtained by reacting a diamine compound represented by the following general formula (8) with a compound represented by R—OH to form a diester derivative, and then reacting the diester derivative with a carbodiimide compound in the presence of H ２ N-Y-NH ２ Further, the polyamic acid ester can be obtained by reacting a diamine compound represented by the following general formula (8) with a diester derivative: ２ N-Y-NH ２The polyamic acid is then isoimidized in the presence of trifluoroacetic anhydride, and then reacted with a compound represented by R—OH to obtain a polyamic acid. In this case, a part of the tetracarboxylic dianhydride is previously reacted with a compound represented by R—OH to obtain a partially esterified tetracarboxylic dianhydride and H ２ N-Y-NH ２ Alternatively, the compound may be reacted with a diamine compound represented by the following formula to form a polyamic acid.

[0102] Examples of compounds represented by R—OH that can be used in the synthesis of polyamic acid esters include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

[0103] There are no particular restrictions on the molecular weight of the polyamic acid ester, and the weight average molecular weight may be, for example, 10,000 to 200,000, 20,000 to 150,000, or 30,000 to 100,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.

[0104] From the viewpoint of obtaining a cured product with low stress, the weight-average molecular weight of the polyamic acid ester is preferably 20,000 or more, more preferably 30,000 or more, and even more preferably 40,000 or more. The weight-average molecular weight of the polyamic acid ester may be 200,000 or less, 150,000 or less, or 100,000 or less.

[0105] When the structural unit (A) contains at least one of a structural unit derived from a compound represented by chemical formula (A-2) and a structural unit derived from a compound represented by chemical formula (A-4) (preferably when it does not contain a structural unit derived from a compound represented by chemical formula (A-6)), from the viewpoint of obtaining a cured product with low stress, the weight-average molecular weight of the polyamic acid ester is preferably 35,000 or more, more preferably 35,000 or more, and even more preferably 40,000 or more.

[0106] When the structural unit (A) includes a structural unit derived from a compound represented by chemical formula (A-6), the weight-average molecular weight of the polyamic acid ester is preferably 50,000 or more, more preferably 60,000 or more, and even more preferably 70,000 or more, from the viewpoint of obtaining a cured product with low stress.

[0107] The stress when the polyamic acid ester is formed into a cured film may be 30.0 MPa or less, 20.0 MPa or less, 5.0 MPa to 20.0 MPa, or 5.0 MPa to 15.0 MPa.

[0108] The stress of a cured film of polyamic acid ester can be measured as follows. First, 30 parts by mass of polyamic acid ester and 70 parts by mass of a solvent (e.g., 3-methoxy-N,N-dimethylpropanamide) are mixed to obtain a resin composition. The obtained resin composition is applied to a silicon wafer, and the solvent is then volatilized to obtain a coating film with a thickness of approximately 10 μm after curing. The obtained coating film is heat-cured at 350°C for 1 hour in a nitrogen atmosphere to obtain a polyimide film (cured film). The residual stress of the cured polyimide film is measured at room temperature using a stress measurement device.

[0109] <Resin Composition> The resin composition of the present disclosure includes the polyamic acid ester of the present disclosure. The resin composition may include other components in addition to the polyamic acid ester of the present disclosure. Examples of other components include resin components other than the polyamic acid ester of the present disclosure, polymerizable monomers, photopolymerization initiators, thermal polymerization initiators, solvents, sensitizers, stabilizers, coupling agents, surfactants, leveling agents, and rust inhibitors. Examples of resin components other than the polyamic acid ester of the present disclosure include polyamic acid esters other than the polyamic acid ester of the present disclosure and resin components other than the polyamic acid ester.

[0110] The resin composition of the present disclosure may be a photosensitive resin composition or a thermosetting resin composition that is cured by heating. The resin composition of the present disclosure may be, for example, a composition that can be cured by light irradiation, heating, or the like. When the resin composition is a photosensitive resin composition, a patterned cured product may be formed using the photosensitive resin composition.

[0111] A cured product obtained from the resin composition of the present disclosure can be used as an interlayer insulating film, a cover coat layer, or a surface protective film. Furthermore, the cured product can be used as a passivation film, a buffer coat film, etc. Highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (such as multi-die fan-out wafer-level packages) can be manufactured using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, and surface protective film.

[0112] The present disclosure will be described in more detail below based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0113] (Synthesis of Polyamic Acid Ester 1) In a 0.5 liter plastic bottle, 50.0 g (170 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) that had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 384.8 g of 3-methoxy-N,N-dimethylpropanamide ("KJCMPA-100" manufactured by KJ Chemicals Co., Ltd.), and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated as the sBPDA solution. A 0.5-liter flask equipped with a stirrer and a thermometer was charged with 340 g of the sBPDA solution, and then, under ice cooling, 29.7 g (250 mmol) of thionyl chloride was added dropwise using a dropping funnel while maintaining the reaction solution temperature at 10°C or below. After the dropwise addition of thionyl chloride was completed, the mixture was stirred under ice cooling for 2 hours to obtain a solution of sBPDA acid chloride. Next, using the dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the sBPDA acid chloride solution while taking care not to allow the temperature of the reaction solution to exceed 10°C under ice cooling, thereby obtaining a polyamic acid ester 1 solution. This polyamic acid ester 1 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 1. The weight average molecular weight of polyamic acid ester 1 calculated in terms of standard polystyrene was 29,000.

[0114] In the present example, the weight-average molecular weight of the polyamic acid ester was determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, the weight-average molecular weight was measured under the following conditions using a solution prepared by dissolving 0.5 mg of the polyamic acid ester in 1 mL of a solvent [tetrahydrofuran (THF) / dimethylformamide (DMF) = 1 / 1 (volume ratio)].

[0115] - Measurement conditions - Measurement equipment: Shimadzu Corporation SPD-M20A Pump: Shimadzu Corporation LC-20AD Column oven: Shimadzu Corporation: CTO-20A Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 Eluent: THF / DMF = 1 / 1 (volume ratio) LiBr (0.03 mol / L), H ３ P.O. ４ (0.06 mol / L) Flow rate: 1.0 mL / min, Detector: UV 270 nm, Column temperature: 40°C Standard polystyrene: Tosoh TSKgel Standard Polystyrene Types F-1, F-4, F-20, F-80, and A-2500. Calibration curves were prepared using these.

[0116] (Synthesis of polyamic acid ester 2) Polyamic acid ester 2 was obtained in the same manner as in the above (Synthesis of polyamic acid ester 1), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight average molecular weight of polyamic acid ester 2, calculated in terms of standard polystyrene, was 78,000.

[0117] (Synthesis of Polyamic Acid Ester 3) In a 0.5 liter plastic bottle, 50.0 g (170 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride (sBPDA) that had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 384.8 g of 3-methoxy-N,N-dimethylpropanamide ("KJCMPA-100" manufactured by KJ Chemicals Co., Ltd.), and after adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated as the sBPDA solution. In a 0.5-liter plastic bottle, 65.3 g (170 mmol) of the compound represented by chemical formula (A-2) (CpODA), which had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 369.5 g of 3-methoxy-N,N-dimethylpropanamide ("KJCMPA-100" (KJ Chemicals Co., Ltd.)). After adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated the CpODA solution. In a 0.5-liter flask equipped with a stirrer and thermometer, 170 g of the sBPDA solution obtained above and 170 g of the CpODA solution were placed. The blending ratio of CpODA to sBPDA (CpODA:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, under ice cooling, 29.7 g of thionyl chloride was added dropwise using a dropping funnel so that the reaction solution temperature was maintained at 10° C. or less. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of CpODA and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of acid chlorides of CpODA and sBPDA while cooling with ice, taking care not to allow the temperature of the reaction solution to exceed 10°C, thereby obtaining a solution of polyamic acid ester 3.This solution of polyamic acid ester 3 was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 3. The weight average molecular weight of polyamic acid ester 3 calculated in terms of standard polystyrene was 28,000.

[0118] (Synthesis of Polyamic Acid Ester 4) Polyamic acid ester 4 was obtained in the same manner as in the above (Synthesis of Polyamic Acid Ester 3), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight average molecular weight of polyamic acid ester 4, calculated in terms of standard polystyrene, was 40,000.

[0119] (Synthesis of Polyamic Acid Ester 5) In a 0.5-liter plastic bottle, 51.0 g (170 mmol) of the compound (TDA-100) represented by chemical formula (A-1), which had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 383.8 g of KJCMPA-100. After adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated the TDA-100 solution. In a 0.5-liter flask equipped with a stirrer and thermometer, 170 g of the TDA-100 solution obtained above and 170 g of the sBPDA solution obtained in (Synthesis of Polyamic Acid Ester 1) were placed. The blending ratio of TDA-100 to sBPDA (TDA-100:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, under ice-cooling, 29.7 g of thionyl chloride was added dropwise using a dropping funnel so that the reaction solution temperature was maintained at 10°C or below. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice-cooling for 2 hours to obtain a solution of acid chlorides of TDA-100 and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of TDA-100 and sBPDA acid chloride, while cooling on ice and taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 5. This polyamic acid ester 5 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 5. The weight average molecular weight of polyamic acid ester 5, calculated in terms of standard polystyrene, was 25,000.

[0120] (Synthesis of Polyamic Acid Ester 6) Polyamic acid ester 6 was obtained in the same manner as in the above (Synthesis of Polyamic Acid Ester 5), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight average molecular weight of polyamic acid ester 6, calculated in terms of standard polystyrene, was 60,000.

[0121] (Synthesis of Polyamic Acid Ester 7) In a 0.5-liter plastic bottle, 69.1 g (170 mmol) of the compound (BzDAxx) represented by chemical formula (A-5), which had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 365.7 g of KJCMPA-100. After adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated the BzDAxx solution. In a 0.5-liter flask equipped with a stirrer and thermometer, 170 g of the BzDAxx solution obtained above and 170 g of the sBPDA solution obtained in (Synthesis of Polyamic Acid Ester 1) were placed. The blending ratio of BzDAxx to sBPDA (BzDAxx:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, under ice cooling, 29.7 g of thionyl chloride was added dropwise using a dropping funnel so that the reaction solution temperature was maintained at 10° C. or less. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of BzDAxx and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of BzDAxx and sBPDA acid chloride, while cooling on ice and taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 7. This polyamic acid ester 7 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 7. The weight average molecular weight of polyamic acid ester 7, calculated in terms of standard polystyrene, was 27,000.

[0122] (Synthesis of Polyamic Acid Ester 8) Polyamic acid ester 8 was obtained in the same manner as in the above (Synthesis of Polyamic Acid Ester 7), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight average molecular weight of polyamic acid ester 8, calculated in terms of standard polystyrene, was 39,000.

[0123] (Synthesis of Polyamic Acid Ester 9) In a 0.5-liter plastic bottle, 33.7 g (170 mmol) of compound (BT-100) represented by chemical formula (A-4), which had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 401.1 g of KJCMPA-100. After adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated the BT-100 solution. In a 0.5-liter flask equipped with a stirrer and thermometer, 170 g of the BT-100 solution obtained above and 170 g of the sBPDA solution obtained in (Synthesis of Polyamic Acid Ester 1) were placed. The blending ratio of BT-100 to sBPDA (BT-100:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, under ice cooling, 29.7 g of thionyl chloride was added dropwise using a dropping funnel so that the reaction solution temperature was maintained at 10°C or below. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of BT-100 and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of BT-100 and acid chloride of sBPDA, while cooling with ice, taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 9. This polyamic acid ester 9 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 9. The weight average molecular weight of polyamic acid ester 9, calculated in terms of standard polystyrene, was 20,000.

[0124] (Synthesis of Polyamic Acid Ester 10) Polyamic acid ester 10 was obtained in the same manner as in the above (Synthesis of Polyamic Acid Ester 9), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight-average molecular weight of polyamic acid ester 10, calculated in terms of standard polystyrene, was 47,000.

[0125] (Synthesis of Polyamic Acid Ester 11) In a 0.5-liter plastic bottle, 33.3 g (170 mmol) of the compound (CBDA) represented by chemical formula (A-6), which had been dried in a dryer at 160°C for 24 hours, 46.5 g (357 mmol) of 2-hydroxyethyl methacrylate, and 0.183 g of benzoquinone were dissolved in 401.5 g of KJCMPA-100. After adding a catalytic amount of 1,8-diazabicycloundecene, the mixture was stirred at room temperature (25°C) for 24 hours to carry out esterification, yielding a diester solution. This solution was designated as the CBDA solution. In a 0.5-liter flask equipped with a stirrer and thermometer, 170 g of the CBDA solution obtained above and 170 g of the sBPDA solution obtained in (Synthesis of Polyamic Acid Ester 1) were placed. The blending ratio of CBDA to sBPDA (CBDA:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, under ice cooling, 29.7 g of thionyl chloride was added dropwise using a dropping funnel so that the reaction solution temperature was maintained at 10° C. or less. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of CBDA and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of CBDA and sBPDA acid chloride, while cooling on ice and taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 11. This polyamic acid ester 11 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 11. The weight average molecular weight of polyamic acid ester 11, calculated in terms of standard polystyrene, was 46,000.

[0126] (Synthesis of Polyamic Acid Ester 12) Polyamic acid ester 12 was obtained in the same manner as in the above (Synthesis of Polyamic Acid Ester 11), except that the amount of PPD added was changed so that the molar ratio to the acid anhydride was 0.99. The weight-average molecular weight of polyamic acid ester 12, calculated in terms of standard polystyrene, was 89,000.

[0127] (Synthesis of Polyamic Acid Ester 13) A CpODA solution was prepared in the same manner as in (Synthesis of Polyamic Acid Ester 3) described above. 340 g of the CpODA solution was placed in a 0.5-liter flask equipped with a stirrer and a thermometer, and then 29.7 g of thionyl chloride was added dropwise using a dropping funnel under ice cooling so that the reaction solution temperature was maintained at 10° C. or less. After the dropwise addition of thionyl chloride was completed, the mixture was stirred under ice cooling for 2 hours to obtain a solution of acid chloride of CpODA. Next, using a dropping funnel, a solution prepared by dissolving 11.68 g (108.0 mmol) of p-phenylenediamine (PPD), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the CpODA acid chloride solution while cooling on ice, taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 13. This polyamic acid ester 13 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 13. The weight-average molecular weight of polyamic acid ester 13, calculated in terms of standard polystyrene, was 69,000.

[0128] (Synthesis of Polyamic Acid Ester 14) An sBPDA solution and a CpODA solution were prepared in the same manner as in the (Synthesis of Polyamic Acid Ester 3) described above. 170 g of the sBPDA solution obtained above and 170 g of the CpODA solution were placed in a 0.5-liter flask equipped with a stirrer and a thermometer. The blending ratio of CpODA to sBPDA (CpODA:sBPDA) was 0.5:0.5 in terms of the molar equivalents (mol Eq) of the acid anhydride groups. Then, 29.7 g of thionyl chloride was added dropwise using a dropping funnel under ice cooling so that the reaction solution temperature was maintained at 10°C or below. After the dropwise addition of thionyl chloride was completed, the reaction was continued under ice cooling for 2 hours to obtain a solution of acid chlorides of CpODA and sBPDA. Next, using a dropping funnel, a solution prepared by dissolving 28.12 g (108.0 mmol) of 4,4"-diamino-p-terphenyl (DATP), 35.884 g (454 mmol) of pyridine, and 0.082 g (0.757 mmol) of benzoquinone in 69.17 g of KJCMPA-100 was added dropwise to the solution of acid chlorides of CpODA and sBPDA while cooling on ice, taking care not to allow the temperature of the reaction solution to exceed 10°C, to obtain a solution of polyamic acid ester 14. This polyamic acid ester 14 solution was added dropwise to distilled water, and the precipitate was collected by filtration and dried under reduced pressure to obtain polyamic acid ester 14. The weight-average molecular weight of polyamic acid ester 14, calculated in terms of standard polystyrene, was 45,000.

[0129] (Preparation of Resin Composition) Resin Compositions 1 to 14 were prepared using the above-described Polyamic Acid Esters 1 to 14. Each resin composition was prepared using 30 parts by mass of the polyamic acid ester and 70 parts by mass of 3-methoxy-N,N-dimethylpropanamide ("KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)) as a solvent.

[0130] (Stress Measurement) The obtained resin composition was applied to a 6-inch silicon wafer by spin coating and heated on a hot plate at 100°C for 3 minutes to volatilize the solvent, yielding a coating film with a film thickness of approximately 10 μm after curing. This was then heat-cured at 350°C for 1 hour in a nitrogen atmosphere using a vertical diffusion furnace manufactured by Koyo Lindberg, yielding a polyimide film (cured film). The residual stress of the cured polyimide film was measured at room temperature using a thin film stress measurement device FLX-2320 manufactured by KLATencor. The results are shown in Table 1.

[0131] (Elastic Modulus Measurement) A polyimide film (cured film) was obtained using the obtained resin composition in the same manner as in the stress measurement described above. The cured polyimide film was punched into strips to prepare test pieces (width: 10 mm), and the tensile modulus (GPa) was measured using an AGS-100NX manufactured by Shimadzu Corporation, with a chuck length of 20 mm and a tensile speed of 5 mm / min. The results are shown in Table 1. In Table 1, "-" indicates that no data is available.

[0132] (Light Transmittance Measurement) The polyamic acid ester described above was dissolved in a solvent, 3-methoxy-N,N-dimethylpropanamide ("KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)) to prepare a solution for measuring light transmittance with a solids concentration of 0.1% by mass. The light transmittance of the solution at each wavelength was then measured. The results are shown in Figs. 1 and 2 and Table 1. "-" in Table 1 means that no data is available.

[0133] The results of measuring the various physical properties when polyamic acid esters 1 to 14 were used are shown in Table 1. In Table 1, acid anhydride 1 is the acid anhydride that constitutes the structural unit (A1-1) and the structural unit (A1-2), and acid anhydride 2 is the acid anhydride that constitutes the structural unit (A2). In the item for acid anhydride 1, "-" means that the acid anhydride was unused.

[0134]

[0135] 1 and 2 and Table 1, it was confirmed that the solutions of polyamic acid esters 4, 10, and 12 to 14 tended to have superior light transmittance at the same wavelength compared to the solution of polyamic acid ester 2. As shown in Table 1, it was confirmed that increasing the weight-average molecular weight of the polyamic acid ester tended to reduce stress.

Claims

1. A polyamic acid ester comprising a structural unit (A) derived from a tetracarboxylic dianhydride and a structural unit (B) derived from a diamine compound, wherein at least a portion of the structural unit (A) has an unsaturated double bond, and when dissolved in a 3-methoxy-N,N-dimethylpropanamide solution having a solids concentration of 0.1 mass %, the polyamic acid ester has a light transmittance of 10% or more at 380 nm.

2. 2. The polyamic acid ester according to claim 1, wherein the structural unit (A) includes a structural unit (A1-1) in which the two acid anhydride groups contained in the tetracarboxylic dianhydride are not bonded to an aromatic ring.

3. The polyamic acid ester according to claim 1, wherein the structural unit (A) contains a structural unit (A1-2) that does not contain an aromatic ring or in which the ratio of the number of aromatic rings contained in the tetracarboxylic acid dianhydride to the molecular weight of the tetracarboxylic acid dianhydride is less than 0.0068.

4. 3. The polyamic acid ester according to claim 2, wherein a content of the structural unit (A1-1) in the structural unit (A) is 25 mol % or more with respect to the structural unit (A).

5. 4. The polyamic acid ester according to claim 3, wherein a content of the structural unit (A1-2) in the structural unit (A) is 25 mol % or more with respect to the structural unit (A).

6. The polyamic acid ester according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride includes at least one of compounds represented by the following chemical formulas (A-1) to (A-6): 【Chemistry 1】

7. The polyamic acid ester according to any one of claims 1 to 5, wherein the structural unit (A) has a structural unit (A2) in which two acid anhydride groups contained in the tetracarboxylic dianhydride are bonded to an aromatic ring.

8. The polyamic acid ester according to any one of claims 1 to 5, which is a compound having a constitutional unit represented by the following general formula (6): 【Chemistry 2】 (In general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group. R ６ and R ７ are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms; R ６ and R ７ At least one of the above is a group represented by the following general formula (7), and the tetravalent organic group represented by X does not contain an aromatic ring, or if it contains an aromatic ring, the aromatic ring is not bonded to four carbonyl groups. 【Chemistry 3】 (In general formula (7), R ８ ~R １０ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.

9. The polyamic acid ester according to any one of claims 1 to 5, wherein the polyamic acid ester has a weight average molecular weight of 20,000 or more.

10. 6. The polyamic acid ester according to claim 1, which has a light transmittance of 70% or more at 400 nm when dissolved in a 3-methoxy-N,N-dimethylpropanamide solution having a solid content concentration of 0.1% by mass.

11. A resin composition comprising the polyamic acid ester according to any one of claims 1 to 5.

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