TWI818094B - Photosensitive resin composition, method for manufacturing patterned cured product, cured product, interlayer insulating film, cover coating, surface protective film and electronic parts - Google Patents

Abstract

A photosensitive resin composition containing: (A) a polyimide precursor with a polymerizable unsaturated bond; (B) a polymerizable monomer with an aliphatic cyclic skeleton; (C) a photopolymerization initiator ; (D) a compound containing an anthracene structure; and (E) a solvent.

Description

Photosensitive resin composition, manufacturing method of patterned cured product, cured product, interlayer insulating film, cover coating, surface protective film and electronic parts

The present invention relates to a photosensitive resin composition, a method for manufacturing a pattern hardened product, a hardened product, an interlayer insulating film, a cover coating, a surface protective film and electronic parts.

Previously, polyimide or polybenzoxazole, which have excellent heat resistance, electrical properties, mechanical properties, etc., were used for surface protection films and interlayer insulating films of semiconductor devices. In recent years, photosensitive resin compositions that impart photosensitive properties to these resins themselves have been used. When this photosensitive resin composition is used, the manufacturing steps of a patterned cured product can be simplified and complicated manufacturing steps can be shortened. (For example, refer to Patent Document 1)

However, in recent years, the miniaturization of transistors that support high-performance computers has reached the limit of the scaling law. In order to further improve performance or speed, a multilayer device structure in which semiconductor elements are three-dimensionally stacked has attracted attention.

In the built-up device structure, multi-die Fanout Wafer Level Packaging is a package manufactured by sealing multiple dies together in one package. It is different from the previously proposed fan-out wafer level packaging. It is expected to have lower cost and higher performance compared to 1-level packaging (manufactured by sealing one die in one package), so it is attracting attention.

In the production of multi-die fan-out wafer-level packages, low-temperature curability is strongly required from the viewpoint of improving yield by protecting high-performance die or protecting sealing materials with low heat resistance (see, for example, patent documents 2).

Moreover, as a resin composition, a resin composition containing a polyimide precursor is disclosed (for example, refer to Patent Document 3). [Prior art documents] [Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2009-265520 [Patent Document 2] International Publication No. 2008/111470 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-199662

An object of the present invention is to provide a photosensitive resin composition, a method for producing a patterned cured product, and a cured product that can form a good cured product even at low temperature curing of 200° C. or lower and have excellent resolution and patternability after development. , interlayer insulating film, covering coating, surface protective film and electronic parts.

According to the present invention, the following photosensitive resin compositions and the like are provided. 1. A photosensitive resin composition containing: (A) a polyimide precursor having a polymerizable unsaturated bond; (B) a polymerizable monomer having an aliphatic cyclic skeleton; (C) photopolymerization starter; (D) a compound containing an anthracene structure; and (E) a solvent. 2. The photosensitive resin composition according to 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1). [Chemical 1] (In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, the -COOR ₁ group and the -CONH- group are in the ortho position to each other, and the -COOR ₂ group and the -CO- group are in the ortho position to each other. Y ₁ is a divalent aromatic group. _{R 1} and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ₁ and R ₂ At least one of is a group represented by the above formula (2).) [Chemical formula 2] (In formula (2), R ₃ to R ₅ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.) 3. The photosensitive resin as described in 1 or 2 A composition in which the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond and having an aliphatic cyclic skeleton. 4. The photosensitive resin composition according to 3, wherein the component (B) is a polymerizable monomer having two or more groups containing polymerizable unsaturated double bonds and having a fat Family cyclic skeleton. 5. The photosensitive resin composition according to any one of 1 to 3, wherein the component (B) contains a polymerizable monomer represented by the following formula (3). [Chemical 3] (In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1, and n2 is 0 to 2. Integer, n1+n2 is 1 or more. At least one of n1 R ₆ and n2 R ₇ is a base represented by the following formula (4).) [Chemical 4] (In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10.) 6. The photosensitive resin composition according to 5. , where n1+n2 is 2 or 3. 7. The photosensitive resin composition according to any one of 1 to 6, wherein the component (B) contains a polymerizable monomer represented by the following formula (5). [Chemistry 5] 8. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) contains a compound represented by the following formula (31). [Chemical 6] (In formula (31), R ₆₁ is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroaryl group having 5 to 18 atoms. , or a halogen atom, n10 is an integer from 0 to 8.) 9. The photosensitive resin composition according to any one of 1 to 7, wherein the component (D) is selected from the group consisting of dibutoxyanthracene, dibutoxyanthracene, One or more types of the group consisting of methoxyanthracene, diethoxyanthracene, and diethoxyethylanthracene. 10. The photosensitive resin composition according to any one of 1 to 9, further containing (F) a thermal polymerization initiator. 11. The photosensitive resin composition according to any one of 1 to 10, which is used for panel-level packaging. 12. A method for manufacturing a patterned hardened product, comprising: applying the photosensitive resin composition according to any one of 1 to 11 on a substrate and drying it to form a photosensitive resin film; The step of subjecting the patterned resin film to pattern exposure to obtain a resin film; the step of developing the patterned resin film using an organic solvent to obtain a patterned resin film; and the step of subjecting the patterned resin film to heat treatment. 13. The method for manufacturing a patterned hardened product according to 12, wherein the temperature of the heat treatment is 200°C or lower. 14. A cured product obtained by curing the photosensitive resin composition according to any one of 1 to 11. 15. The hardened material according to 14, which is a patterned hardened material. 16. An interlayer insulating film, cover coating, or surface protective film produced using the hardened material described in 14 or 15. 17. An electronic component containing the interlayer insulating film, cover coating or surface protective film according to 16.

According to the present invention, it is possible to provide a photosensitive resin composition, a method for producing a patterned cured product, and a cured product that can form a good cured product even at low temperature curing of 200° C. or lower and have excellent resolution and patternability after development. , interlayer insulating film, covering coating, surface protective film and electronic parts.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, a method for producing a patterned cured product using the same, a cured product, an interlayer insulating film, an overcoat layer, a surface protective film, and an electronic component will be described in detail. In addition, the present invention is not limited to the following embodiments.

In this specification, "A or B" only needs to include either A or B, and may also include both. In addition, in this specification, the term "step" includes not only independent steps, but even when they cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it is included in this term. The numerical range expressed using "～" means the range including the numerical values described before and after "～" as the minimum value and the maximum value respectively. In addition, in this specification, regarding the content of each component in the composition, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, it refers to the multiple substances present in the composition. The total amount of matter. Furthermore, as for the exemplified materials, unless otherwise specified, they may be used individually or in combination of two or more types. The "(meth)acrylic group" in this specification means "acrylic group" and "methacrylic group".

The photosensitive resin composition of the present invention contains: (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as “(A) component”); (B) having an aliphatic cyclic skeleton polymerizable monomer (also called "crosslinking agent") (hereinafter, also called "(B) component"); (C) photopolymerization initiator (hereinafter, also called "(C) component") ; (D) a compound containing an anthracene structure (hereinafter, also referred to as "(D) component"); and (E) solvent (hereinafter, also referred to as "(E) component").

Thereby, even if low-temperature curing is performed at 200° C. or lower, a good cured product can be formed, and the resolution and patterning properties after development are excellent. In addition, as an optional effect, a good cured product can be formed even at low temperature curing of 200° C. or lower, and a cured product with excellent resolution after curing can be formed.

The photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition. In addition, from the viewpoint of photosensitive characteristics during h-ray exposure, the photosensitive resin composition of the present invention is preferably used in a panel level package (for example, it does not have a package substrate, but instead uses a self-made wafer. The terminals are brought out of the rewiring layer of the wiring and connected to the package of the structure of the external terminals). The photosensitive resin composition of the present invention is preferably a material for panel-level packaging or a material for electronic components.

The component (A) is not particularly limited, but is preferably a polyimide that has high transmittance when i-rays are used as the light source during patterning and exhibits high cured product characteristics even when cured at a low temperature of 200° C. or lower. precursor.

Examples of polymerizable unsaturated bonds include carbon-carbon double bonds.

The component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1). Thereby, the i-ray transmittance is high, and even when curing at a low temperature of 200° C. or lower, a good cured product can be formed. The content of the structural unit represented by formula (1) is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, based on all the structural units of component (A). The upper limit is not particularly limited, but may be 100 mol%.

[Chemical 7] (In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, the -COOR ₁ group and the -CONH- group are in the ortho position to each other, and the -COOR ₂ group and the -CO- group are in the ortho position to each other. Y ₁ is a divalent aromatic group. _{R 1} and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ₁ and R ₂ At least one of is a base represented by the formula (2).)

[Chemical 8] (In formula (2), R ₃ to R ₅ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10 (preferably an integer of 2 to 5, more preferably 2 or 3).)

In the tetravalent group having one or more (preferably one to three, more preferably one or two) aromatic groups of X ₁ in the formula (1), the aromatic group may be an aromatic hydrocarbon group or an aromatic hydrocarbon group. It is an aromatic heterocyclic group. An aromatic hydrocarbon group is preferred.

Examples of the aromatic _hydrocarbon group of , divalent to tetravalent bases formed from perylene, etc.

Examples of the tetravalent group having one or more aromatic groups of X ₁ in the formula (1) include, but are not limited to, the tetravalent group of the following formula (6). [Chemical 9] (In formula (6), X and Y each independently represent a divalent group or a single bond that is not conjugated to the benzene ring to which they are bonded. Z is an ether group (-O-) or a thioether group (-S- ) (Preferably -O-).)

In formula (6), the divalent groups of X and Y that are not conjugated with the benzene ring to which they are bonded are preferably -O-, -S-, methylene, and bis(trifluoromethyl)methylene. , or difluoromethylene, more preferably -O-.

The divalent aromatic group of Y ₁ in Formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. Preferred is a divalent aromatic hydrocarbon group.

Examples of the divalent aromatic hydrocarbon group of Y ₁ in the formula (1) include the group of the following formula (7), but are not limited thereto. [Chemical 10] (In formula (7), R ₁₂ to R ₁₉ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, or a monovalent organic group having a halogen atom.)

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, and more preferably having 1 to 6 carbon atoms) of R ₁₂ to R ₁₉ in the formula (7) include methyl and the like. For example, R ₁₂ and R ₁₅ to R ₁₉ may be hydrogen atoms, and R ₁₃ and R ₁₄ may be monovalent aliphatic hydrocarbon groups.

The monovalent organic group having a halogen atom (preferably a fluorine atom) of R ₁₂ to R ₁₉ in the formula (7) is preferably a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having a carbon number of 1 to 10, more preferably (carbon number 1 to 6), trifluoromethyl, etc. can be mentioned.

Examples of aliphatic hydrocarbon groups having 1 to 4 carbon atoms (preferably 1 or 2) for R ₁ and R ₂ in formula (1) include: methyl, ethyl, n-propyl, 2-propyl, n-butyl Key et al.

At least one of R ₁ and R ₂ in formula (1) is a group represented by formula (2), and preferably both R ₁ and R ₂ are groups represented by formula (2).

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms (preferably 1 or 2) for R ₃ to R ₅ in the formula (2) include methyl, ethyl, n-propyl, 2-propyl, and the like. Preferred is methyl.

A polyimide precursor having a structural unit represented by formula (1) can be obtained, for example, by mixing tetracarboxylic dianhydride represented by the following formula (8) and the following formula (9) ) is reacted in an organic solvent such as N-methyl-2-pyrrolidinone to obtain polyamide, and a compound represented by the following formula (10) is added, and in the organic solvent The reaction proceeds to introduce ester groups locally. The tetracarboxylic dianhydride represented by Formula (8) and the diamine-based compound represented by Formula (9) may be used individually by one type, or two or more types may be combined.

[Chemical 11] (In formula (8), X ₁ is a base corresponding to X ₁ in formula (1).)

[Chemical 12] (In formula (9), Y ₁ is as defined in formula (1).)

[Chemical 13] (In Formula (10), R is a group represented by Formula (2).)

The component (A) may have a structural unit other than the structural unit represented by formula (1). Examples of structural units other than the structural unit represented by Formula (1) include the structural unit represented by Formula (11) and the like. [Chemical 14] (In formula (11), X ₂ is a tetravalent group having one or more aromatic groups, the -COOR ₅₁ group and the -CONH- group are in the ortho position to each other, and the -COOR ₅₂ group and the -CO- group are in the ortho position to each other. Y ₂ is a divalent aromatic group. _{R 51} and R ₅₂ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.)

Examples of the tetravalent group having one or more aromatic groups in X ₂ of Formula (11) are the same as the tetravalent group having one or more aromatic groups in X ₁ in Formula (1). Examples of the divalent aromatic group of Y ₂ in the formula (11) include the same divalent aromatic group as the divalent aromatic group of Y ₁ in the formula (1). Examples of the aliphatic hydrocarbon groups having 1 to 4 carbon atoms in R ₅₁ and R ₅₂ in the formula (11) are the same as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms in R ₁ and R ₂ .

The structural unit other than the structural unit represented by Formula (1) may be used individually by 1 type, or in combination of 2 or more types.

The content of structural units other than the structural units represented by formula (1) is preferably less than 50 mol % with respect to all the structural units of component (A).

In component (A), the proportion of carboxyl groups esterified with the group represented by formula (2) relative to all carboxyl groups and all carboxyl esters is preferably 50 mol% or more, more preferably 60 mol% to 100 mol%. %, preferably 70 mol% to 90 mol%.

The molecular weight of component (A) is not particularly limited, but is preferably 10,000 to 200,000 in terms of number average molecular weight. The number average molecular weight can be measured, for example, by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve.

The photosensitive resin composition of the present invention contains (B) a polymerizable monomer having an aliphatic cyclic skeleton (preferably 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms). This can impart hydrophobicity to the cured product that can be formed, thereby suppressing a decrease in the adhesiveness between the cured product and the substrate under high-temperature and humid conditions.

(B) Component preferably contains a group having (preferably two or more) polymerizable unsaturated double bonds (since it can be polymerized by a photopolymerization initiator, (meth)acrylic acid is preferred) (B) is a polymerizable monomer with an aliphatic cyclic skeleton. In order to improve the cross-linking density and photosensitivity and suppress pattern swelling after development, component (B) is preferably a polymerizable monomer containing two to three polymerizable monomers. A saturated double bond base.

The component (B) preferably contains a polymerizable monomer represented by the following formula (3). [Chemical 15] (In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4). n1 is 0 or 1, and n2 is 0 to 2. Integer, n1+n2 is 1 or more (preferably 2 or 3). At least one (preferably two or three) of n1 R ₆ and n2 R ₇ is represented by the following formula (4) base.)

In the case where there are two R ₇ s, the two R _{7 s} may be the same or different.

[Chemical 16] (In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and l is an integer of 0 to 10 (preferably 0, 1, or 2).)

The component (B) more preferably contains a polymerizable monomer represented by the following formula (5). [Chemical 17]

In addition, as the component (B), for example, the following polymerizable monomers can also be used.

[Chemical 18] In formula (12), R ₂₁ to R ₂₄ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (4). n3 is an integer from 1 to 3 (preferably 2 or 3). n4 is an integer from 1 to 3 (preferably 2 or 3). n5 is 0 or 1, n6 is 0 or 1. n5+n6 is 1 or more (preferably 2).

When there are two or more R _21s , the two or more R _21s may be the same or different. When there are two or more R _22s , the two or more R _22s may be the same or different.

At least one (preferably two or three) of n3 R _21s is a group represented by the formula (4). At least one (preferably two or three) of n4 R _22s is a group represented by the formula (4). At least one (preferably two) of n5 R ₂₃ and n6 R ₂₄ is a group represented by the above formula (4).

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms in R ₆ and R ₇ in the formula (3) and R ₂₁ to R ₂₄ in the formula (12) include those having a carbon number of 1 in R ₁ and R ₂ in the formula (1). ~4 aliphatic hydrocarbon groups are the same.

Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms in R ₉ to R ₁₁ in the formula (4) include the same aliphatic hydrocarbon groups having 1 to 3 carbon atoms in R ₃ to R ₅ in the formula (2).

(B) Component may be used individually by 1 type, or in combination of 2 or more types.

The content of component (B) is preferably 1 to 50 parts by mass relative to 100 parts by mass of component (A). From the viewpoint of improving the hydrophobicity of the hardened material, the content is more preferably 3 to 50 parts by mass, and even more preferably 5 to 35 parts by mass. When it is within the above range, it is easy to obtain a practical relief pattern, and it is easy to suppress post-development residues in unexposed areas.

Preferred examples of the component (C) include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, and dibenzylketone. Benzophenone derivatives such as quinone, 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenylketone and other acetophenone derivatives, thiophene Thioxanthone derivatives such as xanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benzyl-β-methyl Benzyl derivatives such as oxyethyl acetal, benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl) oxime, 1- Phenyl-1,2-propanedione-2-(O-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, 1- Phenyl-1,2-propanedione-2-(O-benzyl)oxime, 1,3-diphenylglycerol-2-(O-ethoxycarbonyl)oxime, 1-phenyl -3-Ethoxyglycerol-2-(O-benzoyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-,1-(O-acetyl oxime), oxime esters such as compounds represented by the following formula, etc., but are not limited to these. [Chemical 19]

Especially in terms of light sensitivity, oxime esters are preferred.

(C) component preferably contains (C1) a compound represented by the following formula (15) (hereinafter, also referred to as "(C1) component"). The component (C1) is preferably a photosensitive agent that has a higher sensitivity to actinic rays than the component (C2) described below, and is highly sensitive.

[Chemistry 20] In formula (15), R _11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5. R _12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. R _13A and R _14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), a phenyl group or a tolyl group. When a1 is an integer of 2 or more, R _11A may be the same or different.

R _11A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. a1 is preferably 1. R _12A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group. R _13A and R _14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

Examples of the compound represented by formula (15) include a compound represented by the following formula (15A), which is available as "IRGACURE OXE 02" manufactured by BASF Japan Co., Ltd. Get. [Chemistry 21]

In addition, component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as "component (C2)"). The component (C2) is preferably a photosensitizer whose sensitivity to actinic rays is lower than that of the component (C1), and is preferably a standard sensitivity.

[Chemistry 22] In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, and R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably, alkyl group having 1 to 4 carbon atoms), and Alkoxy group with 1 to 12 carbon atoms (preferably with 1 to 4 carbon atoms), cycloalkyl group with 4 to 10 carbon atoms, phenyl or tolyl group, c1 is an integer of 0 to 5. When c1 is an integer of 2 or more, R _21A may be the same or different.

c1 is preferably 0. R _22A is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. R _23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and even more preferably a methoxy group or an ethoxy group.

Examples of the compound represented by formula (16) include a compound represented by the following formula (16A), which is available as "G-1820 (PDO)" manufactured by Lambson Corporation. [Chemistry 23]

(C) Component may be used individually by 1 type, or in combination of 2 or more types.

(C) component preferably contains one or more types selected from the group consisting of (C1) component and (C2) component. Moreover, it is preferable that (C) component contains (C1) component and (C2) component.

The content of component (C) is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of component (A), more preferably 0.1 to 15 parts by mass, and still more preferably 0.2 to 10 parts by mass. When it is within the said range, photo-crosslinking becomes easy to become uniform in the film thickness direction, and it becomes easy to obtain a practical relief pattern.

When component (C1) is contained, the content of component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.07 to 2.5 parts by mass, and more preferably 100 parts by mass of component (A). 0.09 parts by mass to 1.0 parts by mass.

When component (C2) is contained, the content of component (C2) is usually 0.5 to 15.0 parts by mass, preferably 1.0 to 13.0 parts by mass relative to 100 parts by mass of component (A).

When component (C1) and component (C2) are contained, it is preferable that the content of component (C1) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of component (A), and the content of component (C2) is preferably It is 0.5 to 15.0 parts by mass relative to 100 parts by mass of component (A).

When the component (C1) and the component (C2) are contained, the mass ratio of the contents of the component (C1) and the component (C2) is preferably 1:30 to 1:70, more preferably 1:35 to 1:65.

From the viewpoint of balancing sensitivity and resolution, component (D) preferably contains a compound represented by the following formula (31). [Chemistry 24] (In formula (31), R ₆₁ is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroaryl group having 5 to 18 atoms. , or a halogen atom (preferably a fluorine atom), n10 is an integer from 0 to 8 (preferably an integer from 1 to 4, more preferably 2, 3 or 4).

Examples of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 2 to 5) include methyl, ethyl, tert-butyl, n-butyl, and the like. Examples of the alkoxy group having 1 to 10 carbon atoms (preferably 1 to 6, more preferably 2 to 5) include a butoxy group (for example, n-butoxy group), a methoxy group, an ethoxy group, and the like.

Examples of the aryl group having 6 to 18 carbon atoms (preferably 6 to 12, more preferably 6 to 10) include phenyl and naphthyl groups. Examples of the heteroaryl group having 5 to 18 atoms (preferably 5 to 12, more preferably 5 to 10) include pyridyl, quinolyl, carbazolyl, and the like.

In addition, from the viewpoint of balancing solubility in the photosensitive resin composition and photosensitive characteristics, component (D) is preferably dialkoxyanthracene which may have a substituent (for example, 9,10 dialkoxyanthracene), Preferably, it is selected from the group consisting of dibutoxyanthracene (for example, 9,10 dibutoxyanthracene), dimethoxyanthracene (for example, 9,10-dimethoxyanthracene), diethoxyanthracene (for example, 9,10 -diethoxyanthracene), and diethoxyethylanthracene (such as 9,10-dimethoxy-2ethylanthracene). Examples of the substituent include methyl, ethyl, tert-butyl, n-butyl, and the like.

(D) Component may be used individually by 1 type, or in combination of 2 or more types.

The content of component (D) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and still more preferably 0.3 to 5 parts by mass relative to 100 parts by mass of component (A). Within the above range, both the solubility of the photosensitive resin composition and the improvement of the photosensitive characteristics can be achieved.

The photosensitive resin composition of the present invention contains (E) solvent. Examples of the component (E) include N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, and ethyl propionate. Ethyl ester, 3-methylmethoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsairinoxide, hexamethylphosphoramide, Tetramethylene terephthalate, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethylmorpholine, etc., usually as long as other ingredients can be fully dissolved, No special restrictions. Among them, from the viewpoint of excellent solubility of each component and coating properties when forming a photosensitive resin film, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, Propylene glycol monomethyl ether acetate, N,N-dimethylformamide, N,N-dimethylacetamide.

In addition, as the component (E), a compound represented by the following formula (21) can also be used. [Chemical 25] (In the formula, R ₄₁ to R ₄₃ are each independently an alkyl group having 1 to 10 carbon atoms.)

Examples of the alkyl group having 1 to 10 carbon atoms (preferably 1 to 3, more preferably 1 or 3) for R ₄₁ to R ₄₃ in the formula (21) include: methyl, ethyl, n-propyl, Isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, etc. The compound represented by formula (21) is preferably 3-methoxy-N,N-dimethylpropylamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd. )).

(E) Component may be used individually by 1 type, or in combination of 2 or more types. The content of component (E) is not particularly limited, but generally it is 50 parts by mass to 1,000 parts by mass relative to 100 parts by mass of component (A).

From the viewpoint of accelerating the polymerization reaction, the photosensitive resin composition of the present invention may further contain (F) a thermal polymerization initiator (hereinafter, also referred to as "(F) component"). The component (F) is preferably a compound that does not decompose during heating (drying) to remove the solvent during film formation, but decomposes by heating during hardening to generate free radicals, thereby promoting the interaction between the components (B). , or the polymerization reaction of component (A) and component (B). The component (F) is preferably a compound with a decomposition point of 110°C or more and 200°C or less. From the viewpoint of promoting the polymerization reaction at a lower temperature, a compound with a decomposition point of 110°C or more and 175°C or less is more preferred. .

Specific examples include peroxyketones such as methyl ethyl ketone peroxide; 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(tert-hexylperoxy)- Peroxyketals such as trihexyl peroxide) cyclohexane, 1,1-di(tert-butyl peroxide) cyclohexane; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene Hydroperoxides such as alkenyl hydroperoxide and p-methane hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide; dilauryl peroxide, benzyl peroxide, etc. Dihydryl peroxides such as hydroxyl peroxide; peroxydicarbonates such as bis(4-tert-butylcyclohexyl)peroxydicarbonate and bis(2-ethylhexyl)peroxydicarbonate; 3rd Butyl Peroxy-2-Ethylhexanoate, 3rd Hexyl Peroxyisopropyl Monocarbonate, 3rd Butyl Peroxybenzoate, 1,1,3,3-Tetramethylbutyl Peroxyesters such as peroxy-2-ethylhexanoate, bis(1-phenyl-1-methylethyl) peroxide, etc. Examples of commercially available products include the trade names "Percumyl D", "Percumyl P", "Percumyl H" (the above are manufactured by NOF Co., Ltd.), and the like.

When component (F) is contained, the content of component (F) is preferably 0.1 to 20 parts by mass based on 100 parts by mass of component (A). In order to ensure good flux resistance, the content of component (F) is more preferably 0.2. Parts by mass to 20 parts by mass, and more preferably 0.3 parts by mass to 10 parts by mass from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.

The photosensitive resin composition of the present invention may further contain a coupling agent (adhesion aid), a surfactant or a leveling agent, a rust inhibitor, a cross-linking agent other than component (B), a sensitizer, a polymerization inhibitor, and the like.

Usually, the coupling agent reacts with component (A) in the heat treatment after development to undergo cross-linking, or the coupling agent itself polymerizes in the heat treatment step. This can further improve the adhesion between the obtained cured product and the substrate.

Preferred silane coupling agents include compounds having a urea bond (-NH-CO-NH-). Thereby, even when hardening is performed at a low temperature of 200° C. or lower, the adhesion to the substrate can be further improved. In order to achieve excellent development of adhesiveness during hardening at low temperature, a compound represented by the following formula (13) is more preferred. [Chemical 26] (In formula (13), R ₃₁ and R ₃₂ are each independently an alkyl group having 1 to 5 carbon atoms. a is an integer of 1 to 10, and b is an integer of 1 to 3.)

Specific examples of the compound represented by formula (13) include ureamethyltrimethoxysilane, ureamethyltriethoxysilane, 2-ureaethyltrimethoxysilane, and 2-ureaethyltriethoxysilane. Oxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc., preferably 3-Ureapropyltriethoxysilane.

As the silane coupling agent, a silane coupling agent having a hydroxyl group or a glycidyl group can also be used. When a silane coupling agent having a hydroxyl group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used together, the adhesion of the cured product to the substrate during low-temperature curing can be further improved. Examples of the silane coupling agent having a hydroxyl group or a glycidyl group include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, and n-propylphenylsilanediol. Butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanediol, n-propylmethylphenyl Silicone alcohol, isopropyl methylphenyl silicone alcohol, n-butylmethylphenyl silicone alcohol, isobutylmethylphenyl silicone alcohol, tert-butylmethylphenyl silicone alcohol, ethyl n-propylphenyl silicone alcohol, ethyl Cumene, n-butylethyl phenyl silicone, isobutylethyl phenyl silicone, tert-butylethyl phenyl silicone, methyldiphenyl silicone, ethyl di Phenylsilicol, n-propyldiphenylsilicol, isopropyldiphenylsilanol, n-butyldiphenylsilicol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol , phenylsilanetriol, 1,4-bis(trihydroxysilyl)benzene, 1,4-bis(methyldihydroxysilyl)benzene, 1,4-bis(ethyldihydroxysilyl)benzene, 1,4-bis(propyldihydroxysilyl)benzene, 1,4-bis(butyldihydroxysilyl)benzene, 1,4-bis(dimethylhydroxysilyl)benzene, 1,4-bis (diethylhydroxysilyl)benzene, 1,4-bis(dipropylhydroxysilyl)benzene, 1,4-bis(dibutylhydroxysilyl)benzene, and those represented by the following formula (14) compounds, etc. Among them, in order to further improve the adhesiveness with the substrate, the compound represented by formula (14) is preferred.

[Chemical 27] (In formula (14), R ₃₃ is a monovalent organic group having a hydroxyl group or a glycidyl group, R ₃₄ and R ₃₅ are each independently an alkyl group having 1 to 5 carbon atoms. c is an integer of 1 to 10, and d is An integer from 1 to 3.)

Examples of the compound represented by formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, and 2-hydroxyethyltriethoxysilane. Silane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidyloxymethyl Trimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxysilane Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc.

The silane coupling agent having a hydroxyl group or a glycidyl group is preferably a group having a nitrogen atom, and is preferably a silane coupling agent having an amine group or an amide bond. Silane coupling agents having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethyl Oxysilane, bis(2-glycidoxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, etc.

As a silane coupling agent having an amide bond, there may be mentioned a silane coupling agent composed of R ₃₆ -(CH ₂ ) _e -CO-NH-(CH ₂ ) _f -Si(OR ₃₇ ) ₃ (R ₃₆ is a hydroxyl group or a glycidyl group, e and f are each independently an integer of 1 to 3, and R ₃₇ is a compound represented by a methyl, ethyl or propyl group, etc.

One type of silane coupling agent may be used alone, or two or more types of silane coupling agents may be used in combination.

When a silane coupling agent is used, the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 100 parts by mass per 100 parts by mass of component (A) Parts by mass ~ 10 parts by mass.

By including a surfactant or a leveling agent, it is possible to improve coating properties (for example, suppression of streaking (uneven film thickness)) and developability.

Examples of surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc., and commercially available products include List the trade names "Megafac F171", "Megafac F173", and "Megafac R-08" (the above, manufactured by DIC Co., Ltd.); the trade name "Flo" "Fluorad FC430", "Fluorad FC431" (the above, manufactured by Sumitomo 3M Co., Ltd.); trade names "organic siloxane polymer (organic siloxane polymer) KP341", "KBM303", "KBM403" ”, “KBM803” (the above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc.

A surfactant and a leveling agent may be used individually by one type, or two or more types may be combined.

When a surfactant or a leveling agent is included, the content of the surfactant or the leveling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 100 parts by mass relative to 100 parts by mass of the component (A). 5 parts by mass, more preferably 0.05 parts by mass to 3 parts by mass.

By including rust inhibitors, corrosion of copper and copper alloys can be inhibited or discoloration can be prevented. Examples of rust inhibitors include triazole derivatives and tetrazole derivatives. Examples of rust inhibitors include: 5-aminotetrazole (for example, 5-amino-1H-tetrazole), benzotriazole, 1-hydroxybenzotriazole, 1H-benzotriazole-1-acetonitrile , benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, mercaptobenzotriazole, etc. Among these, 5-aminotetrazole, benzotriazole or 1-hydroxybenzotriazole is preferred. One type of rust inhibitor may be used alone, or two or more types may be combined.

When using an anti-rust agent, the content of the anti-rust agent is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 parts by mass relative to 100 parts by mass of the component (A). Parts by mass ~ 3 parts by mass.

By including a cross-linking agent other than component (B), the photosensitive characteristics, cured product properties, etc. can be flexibly adjusted, and in particular, the cured product properties can be significantly changed.

Examples of the crosslinking agent other than component (B) include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol diacrylate. Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethyl acrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane Propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, Tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isotrimer Triacrylate cyanate, ethoxylated trimethacrylate isocyanurate, acryloxyethyl isocyanurate, methylacryloxyethyl isocyanurate, etc.

Cross-linking agents other than the component (B) may be used alone or in combination of two or more.

When a cross-linking agent other than component (B) is contained, the content of the cross-linking agent other than component (B) is preferably 0.01 to 20 parts by mass based on 100 parts by mass of component (A), more preferably 0.05 parts by mass to 15 parts by mass, more preferably 1 part by mass to 12 parts by mass.

Examples of sensitizers include Michelone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-tert-butylanthraquinone, 1,2- Benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis-(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthrone , 1,5-acenaphthylenenaphthalene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-[4-(methylthio)phenyl] -2-morpholinyl-1-propanone, diethyl benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, phenanthrenequinone (phenanthrenequinone), core Riboflavin tetrabutyrate, acridine orange, erythrosine, phenanthrenequinone, 2-isopropylthioanthrone, 2,6-bis(p-diethylamine) Benzylidene)-4-methyl-4-azacyclohexanone, 6-bis(p-dimethylaminobenzylidene)-cyclopentanone, 2,6-bis(p-diethyl) Aminophenylidene)-4-phenylcyclohexanone, aminostyryl ketone, 3-coumarone compound, dicoumarin compound, N-phenylglycine, N-phenyldi Ethanolamine, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, compounds represented by the following formula, etc. [Chemical 28]

One type of sensitizer may be used alone, or two or more types may be used in combination.

When a sensitizer is contained, the compounding amount of the sensitizer is preferably 0.1 to 1.5 parts by mass, more preferably 0.2 to 1.2 parts by mass relative to 100 parts by mass of component (A).

By containing a polymerization inhibitor, good storage stability can be ensured. Examples of the polymerization inhibitor include radical polymerization inhibitors, radical polymerization inhibitors, and the like.

Examples of polymerization inhibitors include: 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dioxide, p-methoxy phenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine (phenothiazine), resorcinol, o-dinitrobenzene, p-dinitrophenyl, m-di Nitrobenzene, phenanthrenequinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, p-benzylaminophenol , nitrosamines, etc.

A polymerization inhibitor may be used individually by 1 type, or in combination of 2 or more types.

When a polymerization inhibitor is contained, the content of the polymerization inhibitor is, from the viewpoint of the storage stability of the photosensitive resin composition and the heat resistance of the obtained cured product, relative to 100 parts by mass of the component (A). Preferably, it is 0.01-30 parts by mass, More preferably, it is 0.01-10 parts by mass, Still more preferably, it is 0.05-5 parts by mass.

The photosensitive resin composition of the present invention essentially contains components (A) to (E) and optional (F) components, coupling agents, surfactants, leveling agents, rust inhibitors, and components other than (B). The cross-linking agent, sensitizer and polymerization inhibitor may also contain other unavoidable impurities within the scope that does not impair the effects of the present invention. The photosensitive resin composition of the present invention may contain, for example, 80 mass% or more, 90 mass% or more, 95 mass% or more, 98 mass% or more, or 100 mass% (A) component ~ (E) component, (A) component ~ (F) component, or (A) component to (E) component, and optional (F) component, coupling agent, surfactant, leveling agent, rust inhibitor, cross-linking agent other than (B) component, sensitizer and polymerization inhibitor .

The cured product of the present invention can be obtained by curing the photosensitive resin composition. The hardened material of the present invention can be used as a patterned hardened material or as a non-patterned hardened material. The film thickness of the hardened material of the present invention is preferably 5 μm to 20 μm.

The method for manufacturing a patterned hardened product of the present invention includes the steps of applying the photosensitive resin composition on a substrate and drying it to form a photosensitive resin film; and subjecting the photosensitive resin film to pattern exposure to obtain a resin. The steps of forming a film; using an organic solvent to develop the resin film after pattern exposure to obtain a patterned resin film; and performing a heat treatment on the patterned resin film. Thereby, a patterned hardened product can be obtained.

The method of producing a patternless cured product includes, for example, a step of forming the photosensitive resin film and a step of performing heat treatment. Furthermore, the step of exposure may also be included.

Examples of substrates include: glass substrates; semiconductor substrates such as Si substrates (silicon wafers); metal oxide insulator substrates such as TiO ₂ substrates and SiO ₂ substrates; silicon nitride substrates; copper substrates; copper alloy substrates, etc.

The coating method is not particularly limited, and a rotator or the like can be used.

Drying can be performed using hot plates, ovens, etc. The drying temperature is preferably 90°C to 150°C, and from the viewpoint of ensuring the dissolution contrast, the drying temperature is more preferably 90°C to 120°C. The drying time is preferably 30 seconds to 5 minutes. Drying can also be performed more than twice. Thereby, a photosensitive resin film obtained by forming the photosensitive resin composition into a film shape can be obtained.

The film thickness of the photosensitive resin film is preferably 5 μm to 100 μm, more preferably 6 μm to 50 μm, further preferably 7 μm to 30 μm.

Regarding pattern exposure, for example, exposure is performed in a predetermined pattern through a photomask. Examples of the actinic rays to be irradiated include ultraviolet rays such as i-rays and h-rays, visible rays, radiation, etc., and i-rays are preferred. As the exposure device, a parallel exposure machine, a projection exposure machine, a stepper machine, a scanning exposure machine, etc. can be used.

By performing development, a resin film on which a pattern is formed (patterned resin film) can be obtained. When using a negative photosensitive resin composition, the unexposed portion is usually removed using a developer. As the organic solvent used as a developer, a good solvent of the photosensitive resin film may be used alone, or a good solvent and a poor solvent may be appropriately mixed and used as the developer. Examples of good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Amine, dimethylsulfoxide, γ-butyrolactone, α-acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone, etc. Examples of poor solvents include toluene, xylene, methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

Surfactants can also be added to the developer. The addition amount is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the developer.

The development time can be set to twice the time until the photosensitive resin film is immersed and completely dissolved, for example. The development time also varies depending on the component (A) used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 20 seconds to 5 minutes from the viewpoint of productivity.

After development, it can also be cleaned with eluent. As the eluent, distilled water, methanol, ethanol, isopropyl alcohol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. can be used alone or in appropriate mixtures. In addition, they can also be used in combination in stages. .

By heat-treating the patterned resin film, a patterned cured product can be obtained. The polyimide precursor of component (A) can cause dehydration and ring-closure reaction through the heat treatment step, and usually becomes the corresponding polyimide.

The temperature of the heat treatment is preferably 250°C or lower, more preferably 120°C to 250°C, further preferably 200°C or lower or 160°C to 200°C. By being within the above range, damage to the substrate or device can be suppressed to a minimum, devices can be produced with good yield, and energy saving in the manufacturing process can be achieved.

The heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. By being within the above range, the cross-linking reaction or the dehydration ring-closure reaction can be sufficiently performed. The environment for the heat treatment may be in the atmosphere or in an inert environment such as nitrogen. From the perspective of preventing oxidation of the patterned resin film, a nitrogen environment is preferred.

Examples of equipment used for heat treatment include quartz tube furnaces, hot plates, rapid annealing furnaces, vertical diffusion furnaces, infrared hardening furnaces, electron beam hardening furnaces, microwave hardening furnaces, and the like.

The hardened material of the present invention can be used as a passivation film, a buffer coating film, an interlayer insulating film, a cover coating, a surface protection film, or the like. Highly reliable semiconductor devices, multilayer wiring boards, and various electronic devices can be manufactured by using at least one selected from the group consisting of the passivation film, buffer coating film, interlayer insulating film, cover coating, surface protective film, etc. , built-up devices (multi-chip fan-out wafer-level packaging, etc.) and other electronic components.

An example of the manufacturing steps of the semiconductor device as the electronic component of the present invention will be described with reference to the drawings. FIG. 1 is a diagram showing the manufacturing steps of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present invention. In FIG. 1 , a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film, except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1 .

Next, a photosensitive resin layer 5 of a chlorinated rubber system, a phenol novolac system, or the like is formed on the interlayer insulating film 4, and is disposed in such a manner that a predetermined portion of the interlayer insulating film 4 is exposed by a known photo etching technique. Window 6A.

The interlayer insulating film 4 exposed in the window 6A is selectively etched, thereby providing the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that does not corrode the first conductor layer 3 exposed from the window 6B but only corrodes the photosensitive resin layer 5 .

Furthermore, a known photo etching technique is used to form the second conductor layer 7 and electrically connect it to the first conductor layer 3 . When forming a multilayer wiring structure of three or more layers, the above steps may be repeated to form each layer.

Next, using the photosensitive resin composition, the window 6C is opened by pattern exposure, and the surface protective film 8 is formed. The surface protective film 8 protects the second conductor layer 7 from external stress, α-rays, and the like, and the obtained semiconductor device has excellent reliability. Furthermore, in the above example, the photosensitive resin composition of the present invention can also be used to form an interlayer insulating film. [Example]

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. In addition, this invention is not limited to the following Example.

Synthesis Example 1 (Synthesis of A1) Mix 7.07 g of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP ) was dissolved in 30 g of N-methyl-2-pyrrolidone (NMP), stirred at 30°C for 4 hours, and then stirred at room temperature overnight to obtain polyamic acid. 9.45 g of trifluoroacetic anhydride was added thereto under water cooling, the mixture was stirred at 45° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added. The reaction liquid is added dropwise to distilled water, and the precipitate is filtered, separated, collected, and dried under reduced pressure to obtain polyimide precursor A1. Under the following conditions, use the Gel Permeation Chromatograph (GPC) method and calculate the number average molecular weight by converting it to standard polystyrene. The number average molecular weight of A1 is 40,000.

The measurement was performed using a solution in which the solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)] was 1 mL per 0.5 mg of A1.

Measuring device: Detector L4000UV manufactured by Hitachi, Ltd. Pump: L6000 manufactured by Hitachi, Ltd. C-R4A Chromatopac manufactured by Shimadzu Corporation Measurement conditions: Column Gelpack GL-S300MDT-5×2 elution Liquid: THF/DMF=1/1 (volume ratio) LiBr (0.03 mol/L), H ₃ PO ₄ (0.06 mol/L) Flow rate: 1.0 mL/min, detector: UV 270 nm

In addition, Nuclear Magnetic Resonance (NMR) measurement was performed under the following conditions to calculate the esterification rate of A1 (the reaction rate between the carboxyl group of ODPA and HEMA). The esterification rate was 80 mol% based on all the carboxyl groups of the polyamic acid (the remaining 20 mol% were carboxyl groups).

Measuring equipment: AV400M manufactured by Bruker BioSpin Magnetic field strength: 400 MHz Reference material: tetramethylsilane (TMS) Solvent: dimethyl sulfoxide (DMSO)

Examples 1 to 9 and Comparative Examples 1 to 3 (Preparation of photosensitive resin composition) The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 3 were prepared according to the components and compounding amounts shown in Table 1 and Table 2. The compounding amounts in Tables 1 and 2 are parts by mass of each component relative to 100 parts by mass of A1.

The ingredients used are described below. As component (A), A1 obtained in Synthesis Example 1 was used.

(B) Component: Polymerizable monomer B1 having an aliphatic cyclic skeleton: A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula B1 ) [Chemicalization 29]

(C) Component: Photopolymerization initiator C1: IRGACURE OXE 02 (manufactured by BASF Japan Co., Ltd., ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole) -3-yl]-,1-(O-acetyl oxime)) C2: G-1820 (PDO) (manufactured by Lambson Co., Ltd., 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime)

(D) Ingredients D1: 9,10 dibutoxyanthracene (manufactured by Kawasaki Chemical Industry Co., Ltd.)

(E) Component: Solvent E1: N-methyl-2-pyrrolidinone E2: KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd., a compound represented by the following formula E2) [Chemical 30]

(F) Component: Thermal polymerization initiator F1: Percumyl D (manufactured by NOF Co., Ltd., bis(1-phenyl-1-methylethyl) peroxide, represented by the following formula represented compound) [Chemical 31]

(B) Cross-linking agent other than components ATM-4E: Ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a compound represented by the following formula (n11+n12+n13+n14 is 4) ) [Chemical 32]

Sensitizer BCIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured by Hampford Research, manufactured by compound represented by the formula) [Chemical 33]

Leucochrome LCV: Leucocrystal Violet (manufactured by Yamada Chemical Industry Co., Ltd., a compound represented by the following formula) [Chemical 34]

EMK: 4,4'-bis(diethylamino)benzophenone

Polymerization inhibitor Taobn: 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]-non-2-ene-2,3-dioxide (Hemford Research ( Hampford Research Company)

Rust inhibitor 5Atz: 5-amino-1H-tetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)

Then auxiliary UCT-801: 3-ureidopropyltriethoxysilane (manufactured by United Chemical Technologies)

(Measurement of residual film rate after development 1) Using a coating device Act8 (manufactured by Tokyo Electronics Co., Ltd.), the obtained photosensitive resin composition was spin-coated on a silicon wafer, and dried at 100°C for 2 minutes. , dry at 110° C. for 2 minutes to form a photosensitive resin film with a dry film thickness of 7 μm to 15 μm. The development time was set to twice the time until the obtained photosensitive resin film was immersed in cyclopentanone and completely dissolved. In addition, a photosensitive resin film was produced in the same manner as above, and the obtained photosensitive resin film was irradiated with i-rays of 200 mJ/cm ² using an i-ray stepper FPA-3000iW (manufactured by Canon Co., Ltd.). rays for exposure. Using Act8, the exposed resin film is subjected to liquid development in cyclopentanone for the specified development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a resin film. Regarding the film thickness after heating on a hot plate at 110°C for 2 minutes and the film thickness after development, a part of the film was scratched to expose the silicon wafer, and a contact needle profilometer Dektak 150 was used. (manufactured by Bruker) and measure the height from the exposed silicon wafer surface to the film surface (the film thickness is measured in the same manner below). The film thickness after development of 10 μm was divided by the film thickness after heating on a hot plate at 110° C. for 2 minutes, and the remaining film rate after development was calculated as a percentage. The case where the residual film rate after development is 55% to 100% is designated as A, the case where it is 40% or more and less than 55% is designated as B, and the case where the residual film rate after development is 0% or more and less than 40% is designated as C. The results are shown in Table 1 and Table 2.

(Manufacture of hardened materials 1) Regarding Examples 1 to 9, a vertical diffusion furnace μ-TF (manufactured by Koyo Thermo Systems Co., Ltd.) was used to measure the residual film rate after development at 175°C in a nitrogen atmosphere. The obtained resin film is heated for 1 hour to obtain a hardened product (film thickness after hardening is 7 μm to 10 μm). Regarding Examples 1 to 9, good cured products were obtained.

(Measurement 2 of the remaining film rate after development) Using the coating device Act8, spin-coat the photosensitive resin composition on the silicon wafer, dry it at 100°C for 2 minutes, and then dry it at 110°C for 2 minutes. A photosensitive resin film with a dry film thickness of 7 μm to 15 μm is formed. The development time was set to twice the time until the obtained photosensitive resin film was immersed in cyclopentanone and completely dissolved. In addition, a photosensitive resin film was produced in the same manner as above, and the obtained photosensitive resin film was subjected to mask aligner MA-8 (manufactured by SUSS MicroTec) using an h-ray bandpass filter. ) for exposure by irradiating h-rays of 200 mJ/ ^cm2 . Using Act8, the exposed resin film is subjected to liquid development in cyclopentanone for the specified development time, and then rinsed with PGMEA to obtain a resin film. The film thickness after heating on a hot plate at 110° C. for 2 minutes and the film thickness after development were measured in the same manner as in Measurement 1 of the residual film rate after development. The film thickness after development of 10 μm was divided by the film thickness after heating on a hot plate at 110° C. for 2 minutes, and the remaining film rate after development was calculated as a percentage. The case where the residual film rate after development is 55% to 100% is designated as A, the case where it is 40% or more and less than 55% is designated as B, and the case where the residual film rate after development is 0% or more and less than 40% is designated as C. The results are shown in Table 1 and Table 2.

(Manufacture of hardened material 2) Regarding Examples 1 to 9, the resin film obtained in Measurement 2 of the residual film ratio after development was heated at 175° C. for 1 hour using a vertical diffusion furnace μ-TF in a nitrogen atmosphere to obtain a cured product (after curing Film thickness is 7 μm ~ 10 μm). Regarding Examples 1 to 9, good cured products were obtained.

(Patterning evaluation) Using the coating device Act8, the photosensitive resin composition was spin-coated on the silicon wafer, dried at 100°C for 2 minutes, and then dried at 110°C for 2 minutes to form a dry film thickness of 7 μm～15 μm photosensitive resin film. The development time was set to twice the time until the obtained photosensitive resin film was immersed in cyclopentanone and completely dissolved. In addition, a photosensitive resin film was produced in the same manner as above, and the obtained photosensitive resin film was subjected to mask aligner MA-8 (manufactured by SUSS MicroTec) using an h-ray bandpass filter. ) Expose by irradiating h-rays of 500 mJ/cm ² in a prescribed pattern (10 μm line and space pattern). Using Act8, the exposed resin film is subjected to liquid development in cyclopentanone for the specified development time, and then rinsed with PGMEA to obtain a patterned resin film. The obtained patterned resin film was observed with an optical microscope, and the case where there was no peeling in the line pattern was designated as A, the case where even one line pattern was peeled off was designated as B, and the case where patterning could not be performed was designated as C. The results are shown in Table 1 and Table 2.

(Manufacturing of patterned hardened materials) The obtained resin film was heated at 175°C for 1 hour using a vertical diffusion furnace μ-TF in a nitrogen atmosphere to obtain a patterned hardened product (film thickness after hardening: 10 μm). Regarding Examples 1 to 9, good cured products were obtained.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 (A) Ingredients A1 100 100 100 100 100 100 100 100 100 (B) Ingredients B1 25 25 25 25 25 25 25 25 25 (C) Ingredients C1 - - - 0.1 0.1 - - 2 2 C2 6 9 12 5 5 6 9 - - (D) Ingredients D1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (E) Ingredients E1 165 165 165 160 - 165 165 165 165 E2 - - - - 160 - - - - (F) Ingredients F1 2 2 2 2 2 2 2 2 2 (B) Cross-linking agents other than ingredients ATM-4E 10 10 10 10 10 10 10 10 10 Sensitizer BCIM - - - - - - - - - Leucoplast pigment LCV - - - - - 0.5 0.5 - - EMK 0.5 0.5 0.5 0.4 0.4 0.5 0.5 0.5 - Polymerization inhibitor Taobn 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Rust inhibitor 5Atz 2 2 2 2 2 2 2 2 2 Then auxiliary UCT-801 3 3 3 3 3 3 3 3 3 Residual film rate after development 1 A A A A A A A A A Residual film rate after development 2 A A A A A A A A A patterned evaluation A A A A A A A A A

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 (A) Ingredients A1 100 100 100 (B) Ingredients B1 25 25 25 (C) Ingredients C1 0.2 - - C2 5 - 9 (D) Ingredients D1 - 0.7 - (E) Ingredients E1 160 165 165 E2 - - - (F) Ingredients F1 2 2 2 (B) Cross-linking agents other than ingredients ATM-4E 10 10 10 Sensitizer BCIM - 3.5 - Leucoplast pigment LCV - - - EMK 0.4 - 0.5 Polymerization inhibitor Taobn 0.3 0.3 0.3 Rust inhibitor 5Atz 2 2 2 Then auxiliary UCT-801 3 3 3 Residual film rate after development 1 A C A Residual film rate after development 2 C C B patterned evaluation B C A [Industrial availability]

The photosensitive resin composition of the present invention can be used for interlayer insulating films, cover coatings, surface protective films, etc., and the interlayer insulating films, cover coatings, or surface protective films of the present invention can be used for electronic components, etc.

Several embodiments and/or examples of the present invention have been described in detail above, but those skilled in the art can easily modify these illustrative embodiments and/or examples without substantially departing from the novel teachings and effects of the present invention. /Or the embodiment may be modified in various ways. Therefore, these various modifications are included in the scope of the present invention. The entire contents of the documents described in this specification and the applications that serve as the basis for the priority of the present application under the Paris Treaty are cited.

1:Semiconductor substrate 2: Protective film 3: First conductor layer 4: Interlayer insulation film 5: Photosensitive resin layer 6A, 6B, 6C: Window 7: Second conductor layer 8:Surface protective film

FIG. 1 is a diagram showing the manufacturing steps of an electronic component according to an embodiment of the present invention.

Claims (17)

A photosensitive resin composition containing: (A) a polyimide precursor with a polymerizable unsaturated bond; (B) a polymerizable monomer with an aliphatic cyclic skeleton; (C) a photopolymerization initiator ; (D) a compound containing an anthracene structure; and (E) a solvent, wherein the (D) component contains a compound represented by the following formula (31),

(In formula (31), R ₆₁ is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a heteroaryl group having 5 to 18 atoms. , or halogen atom, n10 is an integer from 0 to 8). The photosensitive resin composition according to claim 1, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1),

(In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, the -COOR ₁ group and the -CONH- group are in the ortho position to each other, and the -COOR ₂ group and the -CO- group are in the ortho position to each other; Y ₁ is a divalent aromatic group; R ₁ and R ₂ are each independently a hydrogen atom, a group represented by the following formula (2), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ₁ and R ₂ At least one of is a group represented by the formula (2);

In formula (2), R ₃ to R ₅ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10). The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer having a group containing a polymerizable unsaturated double bond and having an aliphatic Ring skeleton. The photosensitive resin composition according to claim 3, wherein the component (B) is a polymerizable monomer, and the polymerizable monomer has two or more groups containing polymerizable unsaturated double bonds. And has an aliphatic cyclic skeleton. The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer represented by the following formula (3),

(In formula (3), R ₆ and R ₇ are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4); n1 is 0 or 1, and n2 is 0 to 2 Integer, n1+n2 is 1 or more; at least one of n1 R ₆ and n2 R ₇ is a base represented by the following formula (4);

In formula (4), R ₉ to R ₁₁ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer from 0 to 10). The photosensitive resin composition described in item 5 of the patent application, wherein n1+n2 is 2 or 3. The photosensitive resin composition according to claim 1, wherein the component (B) contains a polymerizable monomer represented by the following formula (5),

The photosensitive resin composition described in item 1 of the patent application, wherein the component (D) is dibutoxyanthracene. The photosensitive resin composition as described in item 1 of the patent application, wherein the component (D) is selected from the group consisting of dibutoxyanthracene, dimethoxyanthracene, diethoxyanthracene and diethoxyethyl One or more species in the group consisting of anthracene. The photosensitive resin composition as described in any one of items 1 to 9 of the patent application, further comprising (F) a thermal polymerization initiator. The photosensitive resin composition described in item 1 of the patent application is used for panel-level packaging. A method for manufacturing a patterned hardened product, including the step of applying the photosensitive resin composition as described in any one of items 1 to 11 of the patent application on a substrate and drying it to form a photosensitive resin film. ; The step of pattern-exposing the photosensitive resin film to obtain a resin film; using an organic solvent to develop the pattern-exposed resin film to obtain a patterned resin film; and heat-treating the patterned resin film. steps. The method for manufacturing a patterned hardened product as described in Item 12 of the patent application, wherein the temperature of the heat treatment is 200°C or lower. A hardened product obtained by hardening the photosensitive resin composition described in any one of items 1 to 11 of the patent application. The hardened product described in Item 14 of the patent application is a patterned hardened product. An interlayer insulating film, cover coating or surface protective film made of the hardened material described in Item 14 or Item 15 of the patent application. An electronic component containing an interlayer insulating film, cover coating or surface protection film as described in Item 16 of the patent application.