KR20210068418A - Photosensitive resin composition, manufacturing method of pattern cured product, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic component - Google Patents

Abstract

(A) The photosensitive resin composition containing the polyimide precursor which has a polymerizable unsaturated bond, (B) a polymerizable monomer, (C) a photoinitiator, (D) a cyclization catalyst, and (E) a solvent.

Description

Photosensitive resin composition, manufacturing method of pattern cured product, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic component

The present invention relates to a photosensitive resin composition, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.

Conventionally, polyimide and polybenzoxazole having excellent heat resistance, electrical properties, mechanical properties, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements. In recent years, the photosensitive resin composition which provided the photosensitive characteristic to these resin itself is used, and if this is used, the manufacturing process of a pattern hardened|cured material can be simplified, and a complicated manufacturing process can be shortened (for example, refer patent document 1). .

However, in recent years, the miniaturization of transistors that have supported the high performance of computers has reached the limit of the scaling law, and a stacked device structure in which semiconductor elements are stacked three-dimensionally in order to further increase performance and speed is attracting attention.

Among the stacked device structures, the multi-die fanout wafer level package (Multi-die Fanout Wafer Level Packaging) is a package manufactured by encapsulating a plurality of dies in one package. Since it is possible to expect lower cost and higher performance than manufacturing by encapsulating one die in one package), it is attracting much attention.

In the production of a multi-die fan-out wafer-level package, low-temperature curability is strongly required from the viewpoint of protecting high-performance die and protecting a sealing material with low heat resistance and improving yield (for example, refer to Patent Document 2) .

Moreover, as a resin composition, the resin composition containing a polyimide precursor is disclosed (for example, refer patent document 3).

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

An object of the present invention is to provide a photosensitive resin composition excellent in storage stability that can form a cured product having excellent mechanical properties even when cured at a low temperature of 230° C. or less, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a cover coat layer, To provide a surface protection film and an electronic component.

ADVANTAGE OF THE INVENTION According to this invention, the following photosensitive resin compositions etc. are provided.

1. (A) a polyimide precursor having a polymerizable unsaturated bond;

(B) a polymerizable monomer;

(C) a photoinitiator;

(D) a cyclization catalyst, and

(E) The photosensitive resin composition containing a solvent.

2. The photosensitive resin composition of 1 whose said (A) component is a polyimide precursor which has a structural unit represented by following formula (1).

(In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, -COOR ₁ group and -CONH- group are ortho-positioned to each other, -COOR ₂ group and -CO- group are mutually ortho-positioned. 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 at least one of _{R 1} and R ₂ This is group represented by said 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 component (D) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'- The photosensitive resin composition as described in 1 or 2 which is 1 or more selected from the group which consists of (4-methylphenyl imino) diethanol.

4. The photosensitive resin composition as described in 1 or 2 in which said (D)component contains the compound represented by following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and among R _31A to R _33A At least one is a monovalent aromatic group. R _31A to R _33A may form a ring between adjacent groups.)

5. The photosensitive resin composition in any one of 1-4 in which said (C)component contains the compound represented by (C1) following formula (15), and (C2) the compound represented by following formula (16).

(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 are each independently represents a hydrogen atom, an alkyl group having 1 to 12 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.)

(In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 4 to 10 carbon atoms of a cycloalkyl group, a phenyl group, or a tolyl group, and 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, respectively.)

6. The photosensitive resin composition in any one of 1-5 in which the said (B) component contains the polymerizable monomer which has aliphatic cyclic skeleton.

7. The photosensitive resin composition in any one of 1-6 in which the said (B) component has group containing a polymerizable unsaturated double bond.

8. The photosensitive resin composition according to 7, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.

9. The photosensitive resin composition in any one of 1-7 in which the said (B) component contains the polymerizable monomer represented by 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 It is an integer, and n1+n2 is equal to or greater than 1. At least one of n1 pieces of R ₆ and n2 pieces of R ₇ is a group 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 l is an integer of 0 to 10.)

10. The photosensitive resin composition of 9 whose n1+n2 is 2 or 3.

11. The photosensitive resin composition in any one of 1-10 in which said (B) component contains the polymerizable monomer represented by following formula (5).

12. (F) The photosensitive resin composition in any one of 1-11 further containing a thermal-polymerization initiator.

13. The photosensitive resin composition in any one of 1-12 containing antioxidant further.

14. The process of apply|coating and drying the photosensitive resin composition in any one of 1-13 on a board|substrate to form a photosensitive resin film;

a step of pattern exposing the photosensitive resin film to obtain a resin film;

A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;

The manufacturing method of the pattern hardened|cured material including the process of heat processing the said pattern resin film.

15. The manufacturing method of the pattern hardened|cured material of 14 whose said heat processing temperature is 230 degrees C or less.

16. Hardened|cured material which hardened the photosensitive resin composition in any one of 1-13.

17. The hardened|cured material of 16 which is a pattern hardened|cured material.

18. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product described in 16 or 17.

19. An electronic component comprising the interlayer insulating film, the cover coat layer, or the surface protective film according to 18.

According to the present invention, a photosensitive resin composition excellent in storage stability capable of forming a cured product having excellent mechanical properties even when cured at a low temperature of 230° C. or lower, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a cover coat layer, a surface A protective film and an electronic component may be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a manufacturing process diagram of the electronic component which concerns on one Embodiment of this invention.

EMBODIMENT OF THE INVENTION Below, embodiment of the photosensitive resin composition of this invention, the manufacturing method of the pattern hardened|cured material using the same, hardened|cured material, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component is demonstrated in detail. In addition, this invention is not limited by the following embodiment.

In this specification, "A or B" may include either one of A and B, or both may be included. In addition, in this specification, the term "process" is included in this term if the desired action of the process is achieved even if it is not clearly distinguishable from an independent process as well as other processes.

The numerical range indicated using "to" indicates a range including the numerical values described before and after "to" as the minimum value and the maximum value, respectively. In addition, in this specification, content of each component in a composition means the total amount of the said some substance which exists in a composition unless it specifically limits when there exist two or more substances corresponding to each component in a composition. In addition, unless it specifically limits, an example material may be used independently and may be used in combination of 2 or more type.

"(meth)acryl group" in this specification means "acryl group" and "methacrylic group".

The photosensitive resin composition of the present invention comprises (A) a polyimide precursor having a polymerizable unsaturated bond (hereinafter, also referred to as “component (A)”), (B) a polymerizable monomer (also referred to as “crosslinking agent”) (hereinafter referred to as “component (A)”). , "(B) component"), (C) photoinitiator (hereinafter also referred to as "(C) component")), (D) cyclization catalyst (hereinafter also referred to as "(D) component"). , and

(E) contains a solvent (hereinafter also referred to as "(E) component".).

Thereby, even if it is low temperature hardening of 230 degreeC or less, the hardened|cured material excellent in mechanical properties can be formed.

Moreover, storage stability can be improved.

Moreover, as an arbitrary effect, even if it is low temperature hardening of 230 degreeC or less, the hardened|cured material excellent in the cyclization rate can be formed.

As an optional effect, it is possible to improve the sensitivity.

It is preferable that the photosensitive resin composition of this invention is a negative photosensitive resin composition. It is preferable that the photosensitive resin composition of this invention is a material for electronic components.

Although it does not restrict|limit especially as component (A), The polyimide precursor which shows high transmittance|permeability when i-line|wire is used for the light source at the time of patterning and high hardened|cured material even at the time of low temperature hardening of 230 degreeC or less is preferable.

As a polymerizable unsaturated bond, the double bond of carbon-carbon, etc. are mentioned.

(A) It is preferable that a component is a polyimide precursor which has a structural unit represented by following formula (1). Thereby, the transmittance|permeability of i line|wire is high, and it can form favorable hardened|cured material even at the time of low temperature hardening of 230 degreeC or less.

It is preferable that content of the structural unit represented by Formula (1) is 50 mol% or more with respect to all the structural units of (A) component, 80 mol% or more is more preferable, and 90 mol% or more is still more preferable. Do. The upper limit is not particularly limited, and may be 100 mol%.

(In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, -COOR ₁ group and -CONH- group are ortho-positioned to each other, -COOR ₂ group and -CO- group are mutually ortho-positioned. 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 at least one of _{R 1} and R ₂ This is group represented by said 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, m is an integer of 1 to 10, preferably an integer of 2 to 5; More preferably, it is 2 or 3).)

In the tetravalent group having one or more (preferably 1 to 3, more preferably 1 or 2) aromatic groups _{of X 1 in} the formula (1), the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. An aromatic hydrocarbon group is preferred.

_{As an aromatic hydrocarbon group of X 1} in formula (1), a divalent to tetravalent (divalent, trivalent or tetravalent) group formed from a benzene ring, a divalent to tetravalent group formed from naphthalene, and perylene A group of 2-4 valence, etc. are mentioned.

_{As tetravalent group which has one or more aromatic groups of X<1>} of Formula (1), although tetravalent group of the following Formula (6) is mentioned, for example, It is not limited to these.

(In formula (6), X and Y each independently represent a divalent group or single bond that is not conjugated to the benzene ring to which each is bonded. Z is an ether group (-O-) or a sulfide group (-S- ) (-O- is preferred).)

In Formula (6), the divalent group which is not conjugated to the benzene ring to which each is couple|bonded of X and Y is -O-, -S-, a methylene group, a bis(trifluoromethyl)methylene group, or difluoro It is preferable that it is a methylene group, and it is more preferable that it is -O-.

A divalent aromatic hydrocarbon group may be sufficient as the divalent aromatic group _{of Y<1>} of Formula (1), and a divalent aromatic heterocyclic group may be sufficient as it. A divalent aromatic hydrocarbon group is preferable.

_{As a divalent aromatic hydrocarbon group of Y<1>} of Formula (1), although group of the following Formula (7) is mentioned, for example, It is not limited to this.

(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.)

Roneun formula (7) R 1 group of monovalent aliphatic hydrocarbon ₁₂ ~ R ₁₉ (preferably from 1 to 10 carbon atoms, preferably having 1 to 6 carbon atoms more), there may be mentioned a methyl group and the like. For example, R ₁₂ and R ₁₅ to R ₁₉ may be a hydrogen atom, and R ₁₃ and R ₁₄ may be a monovalent aliphatic hydrocarbon group.

_{The monovalent organic group having a halogen atom (preferably a fluorine atom) as R 12} to R _{19 in} the formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 10 carbon atoms). 1-6) are preferable, and a trifluoromethyl group etc. are mentioned.

_{Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms for R 1} and R ₂ in Formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n-butyl group. can

It is preferable that at least one of R<_1> and R<_2> of Formula (1) is group represented by Formula (2), and it is group represented by Formula (2) in both.

A methyl group, an ethyl group, n-propyl group, 2-propyl group etc. are mentioned as a C1-C3 (preferably 1 or 2) aliphatic hydrocarbon group _{of R<3>} -R<_5> of Formula (2). A methyl group is preferred.

The polyimide precursor which has a structural unit represented by Formula (1) is N-methyl-2-p for tetracarboxylic dianhydride represented by following formula (8), and the diamino compound represented by following formula (9), for example. It can be obtained by reacting in an organic solvent such as rolidone to obtain polyamic acid, adding a compound represented by the following formula (10), reacting in an organic solvent, and partially introducing an ester group.

The tetracarboxylic dianhydride represented by Formula (8) and the diamino compound represented by Formula (9) may be used individually by 1 type, and may combine 2 or more types.

(, X ₁ in the formula (8) is a group corresponding to X ₁ in the formula (1).)

(In formula (9), Y ₁ is as defined in formula (1).)

(In formula (10), R is a group represented by formula (2) mentioned above.)

(A) The component may have structural units other than the structural unit represented by Formula (1).

As structural units other than the structural unit represented by Formula (1), the structural unit represented by Formula (11), etc. are mentioned.

(In formula (11), X ₂ is a tetravalent group having one or more aromatic groups, -COOR ₅₁ group and -CONH- group are ortho-positioned to each other, -COOR ₅₂ group and -CO- group are mutually ortho-positioned. 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.)

The same thing as the tetravalent group which has one or more aromatic groups _{of X<1>} of Formula (1) is mentioned as the tetravalent group which has one or more aromatic groups _{of X<2>} of Formula (11).

The same thing as the divalent aromatic group _{of Y<1>} of Formula (1) is mentioned as the divalent aromatic group _{of Y<2>} of Formula (11).

Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms _{for R 51} and R _{52 in} the formula (11) include the same as those for the aliphatic hydrocarbon group having 1 to 4 carbon atoms for _{R 1} and R _{2 .}

Structural units other than the structural unit represented by Formula (1) may be used individually by 1 type, and may combine 2 or more types.

It is preferable that content of structural units other than the structural unit represented by Formula (1) is less than 50 mol% with respect to all the structural units of (A) component.

(A) component WHEREIN: It is preferable that the ratio of the carboxy group esterified by the group represented by Formula (2) with respect to all carboxy groups and all carboxy ester is 50 mol% or more, and it is 60-100 mol% is more preferable, and 70-90 mol% is still more preferable.

Although there is no restriction|limiting in particular in the molecular weight of (A) component, It is preferable that it is 10,000-200,000 in number average molecular weight.

A number average molecular weight can be measured by the gel permeation chromatography method, for example, and can be calculated|required by converting using a standard polystyrene analytical curve.

(B) It is preferable that component has (preferably 2 or more) group (preferably, a (meth)acryl group from the point which can superpose|polymerize by a photoinitiator) containing a polymerizable unsaturated double bond. (B) It is preferable that component is a polymerizable monomer which has group containing two or more polymerizable unsaturated double bonds. It is preferable to have 2-3 groups containing a polymerizable unsaturated double bond for the improvement of a crosslinking density and photosensitivity, and suppression of swelling of a pattern after image development.

Moreover, (B) component may also contain the polymerizable monomer which has functional groups other than the group containing a polymerizable unsaturated double bond. Cyclic ether groups, such as an epoxy group and an oxetane group, etc. are mentioned as a functional group.

It is preferable that component (B) contains the polymerizable monomer which has an aliphatic cyclic skeleton (preferably C4-C15, More preferably, it is 5-12). Thereby, hydrophobicity can be provided to the hardened|cured material which can be formed, and the fall of the adhesiveness between the hardened|cured material and a board|substrate under high temperature and high humidity conditions can be suppressed.

(B) It is preferable that a component contains the polymerizable monomer represented by 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 an integer, and n1+n2 is 1 or more (preferably 2 or 3), _{and at least one (preferably 2 or 3) of n1 R 6} and n2 R ₇ is a group represented by the following formula (4) to be.)

When R ₇ is two, two R ₇ may be the same or different.

(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). )

It is more preferable that (B) component contains the polymerizable monomer represented by following formula (5).

In addition, as (B) component, you may use the following polymerizable monomers, for example.

In formula (12), R ₂₁ to R ₂₄ are each independently a C1-C4 aliphatic hydrocarbon group or a group represented by the formula (4). n3 is an integer of 1-3 (preferably 2 or 3). n4 is an integer of 1-3 (preferably 2 or 3). n5 is 0 or 1, and n6 is 0 or 1. n5+n6 is 1 or more (preferably 2).

When R ₂₁ is the presence of two or more, 2 or more and R ₂₁ may be the same, or different.

When R ₂₂ is the presence of two or more, two or more of R ₂₂ may be the same and, or different.

At least one (preferably 2 or 3) of n3 pieces of R ₂₁ is a group represented by the formula (4).

At least one (preferably 2 or 3) of n4 pieces of R ₂₂ is a group represented by the formula (4).

At least one (preferably 2) of n5 pieces of R ₂₃ and n6 pieces of R ₂₄ is a group represented by the formula (4).

As 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), R 1} and R _{2 in} the formula (1) are aliphatic hydrocarbons having 1 to 4 carbon atoms The same thing as the group can be mentioned.

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

(B) The component may contain polymerizable monomers other than the polymerizable monomer which has an aliphatic cyclic skeleton. Thereby, the hardened|cured material which has favorable mechanical properties can be obtained.

Examples of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, penta Erythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxy Sihwa pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryloyloxyethyl isocyanurate, methacryloyloxyethyl isocyanurate, Ethylene oxide (EO) modified bisphenol A diacrylate (For example, as a commercial item, FA324A (made by Hitachi Kasei Corporation)) etc. are mentioned.

(B) A component may be used individually by 1 type, and may combine 2 or more types.

The component (B) preferably contains a polymerizable monomer other than a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer having an aliphatic cyclic skeleton from the viewpoint of obtaining good mechanical properties and photosensitive properties.

When polymerizable monomers other than a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer having an aliphatic cyclic skeleton are included, the content of the polymerizable monomer having an aliphatic cyclic skeleton is 1 with respect to 100 parts by mass of the component (A) ~40 parts by mass is preferred. From a viewpoint of improving the hydrophobicity of hardened|cured material, More preferably, it is 5-35 mass parts. As for content of polymerizable monomers other than the polymerizable monomer which has an aliphatic cyclic skeleton, 1-20 mass parts is preferable with respect to 100 mass parts of (A) component. From a viewpoint of improving the hydrophobicity of hardened|cured material, More preferably, it is 5-15 mass parts.

As for content of (B) component, 1-50 mass parts is preferable with respect to 100 mass parts of (A) component. From a viewpoint of improving the hydrophobicity of hardened|cured material, More preferably, it is 3-50 mass parts, More preferably, it is 5-40 mass parts.

When it is in the said range, it is easy to obtain a practical relief pattern, and it is easy to suppress the residual after image development of an unexposed part.

(C) As a component, For example, benzophenone derivatives, such as benzophenone, o-benzoyl methyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone;

acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and 1-hydroxycyclohexylphenyl ketone;

thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and diethylthioxanthone;

benzyl derivatives such as benzyl, benzyldimethyl ketal, and benzyl-β-methoxyethyl 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-benzoyl)oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) Although oxime esters, such as a compound represented by -9H-carbazol-3-yl]-, 1-(O-acetyloxime), and a following formula, are mentioned preferably, It is not limited to these.

In particular, the point of photosensitivity to oxime esters are preferable.

(C) It is preferable that component (C1) contains the compound (Hereinafter, it is also called "(C1) component".) represented by following formula (15).).

(C1) It is preferable that the sensitivity with respect to actinic light is higher than the component (C2) mentioned later, and, as for a component, it is preferable that it is a high-sensitivity photosensitizer.

In formula (15), R _11A is a C1-C12 alkyl group, and a1 is an integer of 0-5. 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, respectively.

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.

As a compound represented by Formula (15), the compound represented by following formula (15A) is mentioned, for example, It can obtain as "IRGACURE OXE 02" by BASF Japan Corporation.

Moreover, it is preferable that (C) component contains (C2) the compound represented by following formula (16) (Hereinafter, it is also called "(C2) component".).).

(C2) It is preferable that the sensitivity with respect to actinic light is lower than the component (C1), and, as for component, it is preferable that it is a photosensitizer of a standard sensitivity.

In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), and 1 to 12 carbon atoms of an alkoxy group (preferably having 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group, and 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, respectively.

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, still more preferably a methoxy group or an ethoxy group.

As a compound represented by Formula (16), the compound represented by following formula (16A) is mentioned, for example, It can obtain as "G-1820(PDO)" by Lambson company.

(C) A component may be used individually by 1 type, and may combine 2 or more types.

It is preferable that (C) component contains 1 or more chosen from the group which consists of (C1) component and (C2) component.

Moreover, it is preferable that (C)component contains (C1) component and (C2) component.

(C) As for content of component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-5 mass parts.

When it exists in the said range, photocrosslinking becomes easy to become uniform in a film thickness direction, and it becomes easy to obtain a practical relief pattern.

When (C1) component is contained, content of (C1) component is 0.05-5.0 mass parts with respect to 100 mass parts of (A) component normally, Preferably it is 0.07-2.5 mass parts, More preferably, it is 0.09. ~1.0 parts by mass.

(C2) When containing a component, content of (C2) component is 0.5-15.0 mass parts with respect to 100 mass parts of (A) component normally, Preferably it is 1.0-15.0 mass parts.

When (C1) component and (C2) component are contained, content of (C1) component is 0.05-5.0 mass parts with respect to 100 mass parts of (A) component, and content of (C2) component is (A) component It is preferable in it being 0.5-15.0 mass parts with respect to 100 mass parts.

When (C1) component and (C2) component are contained, the mass ratio of content of (C1) component and (C2) component becomes like this. Preferably it is 1:2-1:15, More preferably, it is 1:3-1. :10.

The photosensitive resin composition of this invention contains (D) a cyclization catalyst.

(D) component is 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenyl Preferably at least one selected from the group consisting of ethanolamine, 4-phenylmorpholine and 2,2'-(4-methylphenylimino)diethanol, N-phenyldiethanolamine, N-methylaniline, N-ethyl At least one selected from the group consisting of aniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-(4-methylphenylimino)diethanol is more preferable.

(D) It is preferable that a component contains the compound represented by following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and among R _31A to R _33A At least one (preferably one) is a monovalent aromatic _{group.R 31A} to R _33A represent a 5-membered ring that may have a substituent (for example, a methyl group, a phenyl group) between adjacent groups, or 6-membered ring) may be formed.)

Preferably _{, at least one of R 31A} to R _33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group.

Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms _{) of R 31A} to R _{33A in} the formula (17) include a methyl group and an ethyl group.

As the monovalent aliphatic hydrocarbon group having a hydroxyl group _{of R 31A} to R _33A in Formula (17), one or more (preferably 1 to 3) hydroxyl groups are bonded to the _{monovalent aliphatic hydrocarbon group of R 31A} to R _33A and the like. Specifically, a methylol group, a hydroxyethyl group, etc. are mentioned. A hydroxyethyl group is preferred.

_{The monovalent aromatic group of R 31A} to R _{33A in} the formula (17) may be a monovalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms), or a monovalent aromatic heterocyclic group. . A monovalent aromatic hydrocarbon group is preferable.

A phenyl group, a naphthyl group, etc. are mentioned as a monovalent|monohydric aromatic hydrocarbon group.

_{The monovalent aromatic group of R 31A} to R _33A in Formula (17) may have a substituent. Examples of the substituent include _{the same monovalent aliphatic hydrocarbon group as R 31A} to R _{33A in} the above formula (17) and the monovalent aliphatic hydrocarbon group having a hydroxyl group _{as R 31A} to R _{33A in the above formula (17).} have.

(D) A component may be used individually by 1 type, and may combine 2 or more types.

(D) As for content of component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component from a viewpoint of an imidation rate or a sensitivity improvement. From a viewpoint of storage stability, More preferably, it is 0.3-15 mass parts, More preferably, it is 0.5-10 mass parts.

The photosensitive resin composition of this invention contains the (E) solvent.

(E) As the component, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3- Methyl methoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylsulfone, cyclohexanone, cyclopentanone, diethylketone, diethyl ketone Isobutyl ketone, methyl amyl ketone, N-dimethyl morpholine, etc. are mentioned, Usually, if other components can be fully dissolved, there will be no restriction|limiting in particular.

Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N from the viewpoint of excellent solubility of each component and applicability at the time of forming a photosensitive resin film. -Dimethylformamide and N,N-dimethylacetamide are preferably used.

In addition, as (E) component, you may use the compound represented by following formula (21).

(Wherein, 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) _{of R 41} to R ₄₃ in formula (21) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , n-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. are mentioned.

The compound represented by the formula (21) is preferably 3-methoxy-N,N-dimethylpropanamide (eg, trade name “KJCMPA-100” (manufactured by KJ Chemicals)).

(E) A component may be used individually by 1 type, and may combine 2 or more types.

Although content of (E) component is not specifically limited, Generally, it is 50-1000 mass parts with respect to 100 mass parts of (A) component.

The photosensitive resin composition of this invention may further contain the (F) thermal-polymerization initiator (henceforth "(F) component".) from a viewpoint of polymerization reaction acceleration|stimulation.

As the component (F), it is not decomposed by heating (drying) to remove the solvent at the time of film formation, but is decomposed by heating during curing to generate radicals, (B) components each other, or (A) component and ( B) A compound that promotes the polymerization reaction of the component is preferred.

(F) The decomposition point, a compound of 110 degreeC or more and 200 degrees C or less is preferable, From a viewpoint of accelerating|stimulating a polymerization reaction at lower temperature, the compound of 110 degreeC or more and 175 degrees C or less is more preferable.

Specific examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy) ) cyclohexane, peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, p-menthanhide Hydroperoxides such as loperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di(4 Peroxydicarbonate such as -t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, peroxyesters such as t-butylperoxybenzoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; bis(1-phenyl-1-methylethyl)peroxide; and the like. can As a commercial item, "Percumyl D", "Percumyl P", "Percumyl H" (above, Nichiyu Corporation make), etc. are mentioned as a commercial item.

When the component (F) is contained, the content of the component (F) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and 0.2 to 20 parts by mass to ensure good flux resistance. More preferably, 0.3-10 mass parts is still more preferable from a viewpoint of the solubility fall suppression by decomposition|disassembly at the time of drying.

The photosensitive resin composition of this invention may further contain antioxidant. By containing antioxidant, the oxygen radical and peroxide radical which generate|occur|produce in high temperature storage or reflow process can be supplemented, and the fall of adhesiveness (adhesion property) can be suppressed more. Moreover, oxidation of the electrode at the time of an insulation reliability test can be suppressed, and diffusion from an electrode to a resin film or a pattern resin film can be suppressed.

Antioxidants include N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide, N,N'-bis -3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6- dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione;

2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'- Butylidene-bis (3-methyl-6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2, 2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-t-butyl -4-hydroxy-hydrocinnamamide), isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris[4-triethyl Methyl-3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 2,2'-methylene-bis( 4-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-ethyl-6-t-butylphenol),

Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl -4-hydroxybenzyl)benzene, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6- (1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4 ,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine- 2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimethylbenzyl]-1,3 ,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2-methylbenzyl)-1, 3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione;

Pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-) t-Butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6-trimethylbenzyl)-1,3,5- Triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-6-ethyl-3-hydroxyl- 2,5-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-5, 6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris( 4-t-Butyl-6-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione;

1,3,5-tris(4-t-butyl-5-ethyl-3-hydroxy-2-methylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H )-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H, 5H)-trion, and

1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid etc. are mentioned.

An antioxidant may be used individually by 1 type, and may combine 2 or more types.

When antioxidant is included, as for content of antioxidant, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.1-5 mass parts. is wealth

The photosensitive resin composition of this invention may contain a coupling agent (adhesion auxiliary agent), surfactant, or a leveling agent, a rust preventive agent, a polymerization inhibitor, etc. further.

Usually, in the heat processing after image development, a coupling agent reacts with (A) component and bridge|crosslinks, or in the process of heat-processing, coupling agent itself superposes|polymerizes. Thereby, the adhesiveness of the hardened|cured material obtained and a board|substrate can be improved more.

As a preferable silane coupling agent, the compound which has a urea bond (-NH-CO-NH-) is mentioned. Thereby, even when hardening is performed under the low temperature of 230 degreeC or less, adhesiveness with a board|substrate can be improved further.

Since it is excellent in adhesive expression at the time of hardening at low temperature, the compound represented by following formula (13) is more preferable.

(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 the formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3 -Ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, etc. are mentioned, Preferably 3-urea Idopropyltriethoxysilane.

As a silane coupling agent, you may use the silane coupling agent which has a hydroxyl group or a glycidyl group. 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, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol, Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis(tri Hydroxysilyl)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 the compound represented by following formula (14), etc. are mentioned. Especially, in order to improve more especially adhesiveness with a board|substrate, the compound represented by Formula (14) is preferable.

(In formula (14), R ₃₃ is a monovalent organic group having a hydroxyl group or a glycidyl group, and 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.)

As a compound represented by Formula (14), hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxy Propyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltri Ethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4- Glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc. are mentioned.

It is preferable that the silane coupling agent which has a hydroxyl group or a glycidyl group further contains the group which has a nitrogen atom, and the silane coupling agent which further has an amino group or an amide bond is preferable.

Examples of the silane coupling agent further having an amino group include bis(2-hydroxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, and bis(2- Glycidoxymethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxymethyl)-3-aminopropyltrimethoxysilane, etc. are mentioned.

As a silane coupling agent further having an amide bond, R ₃₆ -(CH ₂ ) _e -CO-NH-(CH ₂ ) _f -Si(OR ₃₇ ) ₃ (R ₃₆ is a hydroxy group or a glycidyl group, e and f is each independently an integer of 1 to 3, and R ₃₇ is a methyl group, an ethyl group, or a propyl group).

A silane coupling agent may be used individually by 1 type, and may combine 2 or more types.

When using a silane coupling agent, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a silane coupling agent, 0.3-10 mass parts is more preferable, 1-10 mass parts is still more preferable. .

By including surfactant or leveling agent, applicability|paintability (for example, suppression of striation (uniformity of a film thickness)) and developability can be improved.

Examples of the surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and the like. Megapack F171", "F173", "R-08" (above, manufactured by DIC Corporation), brand names "Florard FC430", "FC431" (above, manufactured by Sumitomo 3M Corporation), brand name "organosiloxane polymer KP341" , "KBM303", "KBM403", and "KBM803" (above, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like.

Surfactant and a leveling agent may be used individually by 1 type, and may combine 2 or more types.

When surfactant or a leveling agent is included, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of surfactant or a leveling agent, 0.05-5 mass parts is more preferable, 0.05-3 mass parts more preferably.

By containing a rust preventive agent, corrosion suppression and discoloration of copper and a copper alloy can be prevented.

As a rust preventive agent, a triazole derivative, a tetrazole derivative, etc. are mentioned, for example.

A rust preventive agent may be used individually by 1 type, and may combine 2 or more types.

When using a rust preventive agent, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of a rust preventive agent, 0.1-5 mass parts is more preferable, 0.5-3 mass parts is still more preferable.

By containing a polymerization inhibitor, favorable storage stability is securable.

As a polymerization inhibitor, a radical polymerization inhibitor, a radical polymerization inhibitor, etc. are mentioned.

Examples of the polymerization inhibitor include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, meta dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, etc. are mentioned.

A polymerization inhibitor may be used individually by 1 type, and may combine 2 or more types.

When it contains a polymerization inhibitor, as content of a polymerization inhibitor, 0.01-30 mass parts is preferable with respect to 100 mass parts of (A) component from a viewpoint of the storage stability of the photosensitive resin composition, and the heat resistance of the hardened|cured material obtained, 0.01 -10 mass parts is more preferable, and 0.05-5 mass parts is still more preferable.

The photosensitive resin composition of the present invention consists essentially of components (A) to (E), and optionally component (F), a coupling agent, a surfactant, a leveling agent, a rust preventive agent and a polymerization inhibitor, which impairs the effect of the present invention You may include other unavoidable impurities in the range not made.

For example, 80 mass % or more, 90 mass % or more, 95 mass % or more, 98 mass % or more, or 100 mass % of the photosensitive resin composition of this invention,

(A) to (E) components,

(A) to (F) components, or

You may consist of (A)-(E) component, and (F) component, a coupling agent, surfactant, a leveling agent, a rust preventive agent, and a polymerization inhibitor arbitrarily.

The hardened|cured material of this invention can be obtained by hardening|curing the above-mentioned photosensitive resin composition.

The hardened|cured material of this invention may be used as a pattern hardened|cured material, and may be used as a pattern-free hardened|cured material.

As for the film thickness of the hardened|cured material of this invention, 5-20 micrometers is preferable.

In the method for producing a pattern cured product of the present invention, the above-described photosensitive resin composition is applied on a substrate and dried to form a photosensitive resin film, pattern exposure of the photosensitive resin film to obtain a resin film, a resin film after pattern exposure, It develops using an organic solvent, the process of obtaining a pattern resin film, and the process of heat-processing a pattern resin film are included.

Thereby, a pattern hardened|cured material can be obtained.

The method of manufacturing the hardened|cured material without a pattern is equipped with the process of forming the photosensitive resin film mentioned above, and the process of heat-processing, for example. You may further provide the process of exposing.

Examples of the substrate include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), _{metal oxide insulator substrates such as TiO 2} substrates and SiO ₂ substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.

Although there is no restriction|limiting in particular in the application|coating method, A spinner etc. can be used and it can carry out.

Drying can be performed using a hot plate, oven, etc.

90-150 degreeC is preferable and, as for drying temperature, 90-120 degreeC is more preferable from a viewpoint of ensuring melt|dissolution contrast.

As for drying time, 30 second - 5 minutes are preferable.

You may perform drying twice or more.

Thereby, the photosensitive resin film which formed the above-mentioned photosensitive resin composition into the film|membrane can be obtained.

5-100 micrometers is preferable, as for the film thickness of the photosensitive resin film, 6-50 micrometers is more preferable, 7-30 micrometers is still more preferable.

Pattern exposure exposes in a predetermined pattern through a photomask, for example.

The actinic light to be irradiated includes, but is not limited to, i-rays and ultraviolet rays such as broadband (BB), visible light, and radiation.

As an exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine, etc. can be used.

By developing, a pattern-formed resin film (patterned resin film) can be obtained. Generally, when a negative photosensitive resin composition is used, an unexposed part is removed with a developing solution.

The organic solvent used as a developing solution can be used individually by the good solvent of the photosensitive resin film as a developing solution, or a good solvent and a poor solvent can be mixed and used suitably.

As good solvents, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone , α-acetyl-γ-butyrolactone, cyclopentanone, cyclohexanone, and the like.

Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.

You may add surfactant to a developing solution. As an addition amount, 0.01-10 mass parts is preferable with respect to 100 mass parts of developing solutions, and 0.1-5 mass parts is more preferable.

The developing time can be doubled as the time until the photosensitive resin film is immersed and completely dissolved, for example.

Although development time changes also with (A) component to be used, 10 second - 15 minutes are preferable, 10 second - 5 minutes are more preferable, From a viewpoint of productivity, 20 second - 5 minutes are still more preferable.

After image development, you may wash|clean with a rinse liquid.

As a rinse solution, distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used individually or in mixture as appropriate, or may be used in combination in stages.

A pattern hardened|cured material can be obtained by heat-processing a pattern resin film.

(A) The polyimide precursor of component raise|generates a dehydration ring-closure reaction by a heat processing process, and turns into a corresponding polyimide normally.

250 degreeC or less is preferable, as for heat processing temperature, 120-250 degreeC is more preferable, 230 degreeC or less or 180-230 degreeC is still more preferable.

By being in the said range, damage to a board|substrate or a device can be suppressed small, it becomes possible to produce a device with good yield, and energy saving of a process can be implement|achieved.

5 hours or less are preferable and, as for heat processing time, 30 minutes - 3 hours are more preferable.

By being within the above range, a crosslinking reaction or a dehydration ring closure reaction can be sufficiently performed.

The atmosphere of the heat treatment may be in the air or in an inert atmosphere such as nitrogen, but from the viewpoint of preventing oxidation of the pattern resin film, a nitrogen atmosphere is preferable.

Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.

The cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.

High reliability semiconductor devices, multilayer wiring boards, various electronic devices, and laminated devices (multi-die pans) using at least one selected from the group consisting of the passivation film, buffer coating film, interlayer insulating film, cover coating layer, and surface protective film. electronic components such as out-wafer level packages) can be manufactured.

An example of the manufacturing process of the semiconductor device which is an electronic component of this invention is demonstrated with reference to drawings.

BRIEF DESCRIPTION OF THE DRAWINGS It is a manufacturing process diagram of the semiconductor device of the multilayer wiring structure which is an electronic component which concerns on one Embodiment of this 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 the first conductor is on the exposed circuit element. Layer 3 is formed. Thereafter, an interlayer insulating film 4 is formed on the semiconductor substrate 1 .

Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film 4, and a window ( 6A) is formed.

The interlayer insulating film 4 to which the window 6A is exposed is selectively etched to form the window 6B.

Then, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.

A second conductor layer 7 is further formed using a known photolithography technique, and electrical connection with the first conductor layer 3 is performed.

When forming a multilayer wiring structure of three or more layers, each layer can be formed by repeating the above-described process.

Next, using the above-mentioned 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-ray, and the like, and the resulting semiconductor device is excellent in reliability.

Moreover, in the said example, it is also possible to form an interlayer insulating film using the photosensitive resin composition of this invention.

Example

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

Synthesis Example 1 (Synthesis of A1)

3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA) 7.07g and 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) 4.12g N-methyl-2- It melt|dissolved in 30 g of pyrrolidone (NMP), and it stirred at 30 degreeC for 4 hours, then at room temperature overnight, and obtained polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, followed by stirring at 45°C for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added thereto. Polyimide precursor A1 was obtained by dripping this reaction liquid to distilled water, filtration-separating a deposit, and drying it under reduced pressure.

The number average molecular weight was calculated|required on the following conditions by standard polystyrene conversion using the gel permeation chromatography (GPC) method. The number average molecular weight of A1 was 40,000.

It was measured using a solution of 1 mL of a solvent [tetrahydrofuran (THF)/dimethylformamide (DMF) = 1/1 (volume ratio)] with respect to 0.5 mg of A1.

Measuring device: Detector L4000UV made by Hitachi, Ltd.

Pump: L6000 made by Hitachi Seisakusho Co., Ltd.

C-R4A Chromatopac manufactured by Shimadzu Corporation

Measurement conditions: Column Gelpack GL-S300MDT-5×2

Eluent: 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, the esterification rate (reaction rate of the carboxy group of ODPA with HEMA) of A1 was computed by performing NMR measurement on the following conditions. The esterification rate was 80 mol% with respect to all the carboxy groups of polyamic acid (the remaining 20 mol% is a carboxy group).

Measuring device: AV400M made by Bruker Biospin

Magnetic field strength: 400 MHz

Reference material: tetramethylsilane (TMS)

Solvent: dimethyl sulfoxide (DMSO)

Examples 1-3 and Comparative Examples 1-5

(Preparation of photosensitive resin composition)

With the component and compounding quantity shown in Table 1, the photosensitive resin composition of Examples 1-3 and Comparative Examples 1-5 was prepared. The compounding quantity of Table 1 is a mass part of each component with respect to 100 mass parts of A1.

Each component used is as follows. (A) As the component, A1 obtained in Synthesis Example 1 was used.

(B) component: polymerizable monomer

B1: A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tricyclodecane dimethanol diacrylate, a compound represented by the following formula B1)

B2: ATM-4E (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated pentaerythritol tetraacrylate, a compound represented by the following formula (n11+n12+n13+n14 is 4)

B3: FA-324A (manufactured by Hitachi Kasei Co., Ltd., EO-modified bisphenol A diacrylate, a compound represented by the following formula B3)

(C) component: photoinitiator

C1: IRUGCURE OXE 02 (BASF Japan Co., Ltd., ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime))

C2: G-1820 (PDO) (Lambson Co., Ltd., 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl) oxime)

(D) Component: Cyclization Catalyst

D1: 2HE (manufactured by Morin Chemical Industries, Ltd., N-phenyldiethanolamine)

(D') component

D2: U-CAT SA810 (San Apro Co., Ltd., compound represented by the following formula D2)

D3: U-CAT SA1 (San Apro Co., Ltd., compound represented by the following formula D3)

D4: 4-hydroxypyridine

(E) Component: Solvent

E1: KJCMPA-100 (manufactured by KJ Chemicals, a compound represented by the following formula E1)

(F) component: thermal polymerization initiator

F1: Percumyl D (manufactured by Nichiyu Corporation, bis(1-phenyl-1-methylethyl)peroxide, a compound represented by the following formula F1)

(Evaluation of sensitivity)

The obtained photosensitive resin composition was spin-coated on a silicon wafer using an application device Act8 (manufactured by Tokyo Electron Corporation), dried at 105°C for 120 seconds, dried at 115°C for 120 seconds, and a dry film thickness of 13 µm. A resin film was formed.

Twice the time until the obtained photosensitive resin film was immersed in cyclopentanone and melt|dissolved completely was set as developing time.

Further, a photosensitive resin film was produced in the same manner as above, and to the obtained photosensitive resin film, using an i-line stepper FPA-3000iW (manufactured by Canon Corporation), i-line of 100 to 1100 mJ/cm 2 was applied to the It was irradiated in a predetermined pattern with an irradiation amount, and exposure was performed.

After developing the resin film after exposure using Act8 in cyclopentanone for the said developing time, propylene glycol monomethyl ether acetate (PGMEA) rinse-cleaned and the pattern resin film was obtained.

The lower limit of the exposure amount used as 80% or more of the film thickness of the photosensitive resin film before exposure was made into sensitivity as the film thickness of the obtained pattern resin film. A result is shown in Table 1.

(Manufacture of pattern cured product 1)

The pattern resin film obtained in the sensitivity evaluation was heated for 2 hours at 200°C in a nitrogen atmosphere using µ-TF (manufactured by Koyo Thermosystems Co., Ltd.) in a vertical diffusion furnace, and the pattern cured product (film thickness after curing 10 µm) was was obtained

(Manufacture of pattern cured product 2)

The patterned resin film obtained by evaluation of sensitivity was heated at 400 degreeC in nitrogen atmosphere using micro-TF in a vertical diffusion furnace for 1 hour, and the pattern hardened|cured material was obtained.

(Evaluation of exchange rate)

About the pattern resin film obtained by evaluation of sensitivity, IR (infrared spectroscopy) spectrum was measured on condition of the following using FT-IR IRAffinity-1S (made by Shimadzu Corporation). Let this value be IR1.

The measurement conditions of the IR spectrum were performed by a transmission method in a measurement range of 400 to 4000 cm ^-1 , and the number of times of integration 16 times.

For the measurement of the IR spectrum, a silicon wafer was used as the substrate. First, about the board|substrate to which the photosensitive resin composition was not apply|coated, it measured and set it as the background. Next, about the resin film part of the pattern resin film, it measured using the said background, and obtained the IR spectrum.

Moreover, IR was measured similarly to the above about the pattern hardened|cured material obtained by manufacture 1 of the pattern hardened|cured material. Let this value be IR2.

About the pattern hardened|cured material obtained by manufacture 2 of the pattern hardened|cured material, IR was measured similarly to the above. Let this value be IR3.

The conversion rate was calculated|required by dividing the value which subtracted IR1 from IR2 by the value which subtracted IR3 from IR1, and set it as a percentage. 65% or more was made into A, and less than 65% was made into B. A result is shown in Table 1.

(Evaluation of storage stability)

About the above-mentioned photosensitive resin composition, within 24 hours after adjustment, it spin-coated on the Si substrate at the rotation speed which becomes the film thickness after drying 13 micrometers, and on a hotplate, 105 degreeC for 120 second, 115 degreeC for 120 second. It was heat-dried and the photosensitive resin film was formed. The silicon wafer was exposed by rubbing a part of the film, and the height from the exposed silicon wafer surface to the film surface was measured using a folding profiler Dektak150 (manufactured by Bruker) (the measurement of the film thickness was the same, and also the same below). Let this be the film thickness (1).

The photosensitive resin composition mentioned above was left still at room temperature (25 degreeC) after adjustment for 14 days. After standing still, spin-coated at the same rotation speed as when the photosensitive resin film for film thickness (1) measurement was formed on the Si substrate, and dried by heating on a hot plate at 105°C for 120 seconds and 115°C for 120 seconds, A photosensitive resin film was formed. In the same manner as above, the film thickness was measured. Let this be the film thickness (2).

A case where the absolute value obtained by subtracting the film thickness (1) from the film thickness (2) was divided by the film thickness (1) to be 5% or less was defined as A. A case exceeding 5% was designated as B. A result is shown in Table 1.

(Manufacture of pattern cured product 3)

The above-mentioned photosensitive resin composition was spin-coated on a Si substrate, and it heat-dried at 105 degreeC for 120 second and 115 degreeC for 120 second on a hotplate, and formed the photosensitive resin film of 12.0-13.0 micrometers.

The obtained photosensitive resin film was subjected to broadband (BB) exposure using a mask aligner MA-8 (manufactured by Juice Microtech), the resin film after exposure was developed with cyclopentanone, and a rectangular patterned resin having a width of 10 mm got a stop

The obtained patterned resin film was hardened for 2 hours at 200 degreeC in nitrogen atmosphere using micro-TF in a vertical diffusion furnace, and the pattern hardened|cured material with a film thickness of 10 micrometers was obtained.

(Evaluation of elongation)

The pattern cured product obtained in Production 3 of the pattern cured product was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured product having a width of 10 mm was peeled from the wafer.

A tensile test was performed on the peeled-off cured product having a width of 10 mm using Autograph AGS-X 100N (manufactured by Shimadzu Corporation). The distance between chucks was 20 mm, the tensile rate was 5 mm/min, the measurement temperature was 18 to 25°C, and each cured product of each Example and Comparative Example was measured three times to obtain the average value of the elongation.

When the average value of elongation was more than 50%, it was set as A, when it was more than 45% and 50% or less, it was set as B, and when it was 45% or less, it was set as C. As a result before PCT (pressure cooker test), it shows in Table 1.

Moreover, the pattern hardened|cured material obtained in manufacture 3 of the above-mentioned pattern hardened|cured material was treated at 121 degreeC, 100RH (Relative Humidity)%, 2 atm using PCT test apparatus HASTEST (Hirayama Corporation make, PC-R8D) for 100 hours. did.

The pattern hardened|cured material was taken out from the PCT test apparatus, the pattern hardened|cured material was peeled similarly to the above, the tensile test was done, and the average value of elongation was calculated|required.

When the average value of elongation was more than 50%, it was set as A, when it was more than 45% and 50% or less, it was set as B, and when it was 45% or less, it was set as C. Table 1 shows the results after PCT. "-" indicates no measurement.

Industrial Applicability

The photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, or a surface protective film, etc., and the interlayer insulating film, a cover coat layer or a surface protective film of the present invention can be used for an electronic component or the like.

Although the embodiments and/or examples of the present invention have been described in some detail above, those skilled in the art can make many changes to these illustrative embodiments and/or examples without substantially departing from the novel teachings and effects of the present invention. easy to apply Accordingly, many of these modifications are included within the scope of the present invention.

All of the documents described in this specification and the application content underlying the priority of the Paris Convention of the present application are incorporated herein by reference.

Claims (19)

(A) a polyimide precursor having a polymerizable unsaturated bond;
(B) a polymerizable monomer;
(C) a photoinitiator;
(D) a cyclization catalyst, and
(E) The photosensitive resin composition containing a solvent. The method of claim 1,
The photosensitive resin composition whose said (A) component is a polyimide precursor which has a structural unit represented by following formula (1).

(In formula (1), X ₁ is a tetravalent group having one or more aromatic groups, -COOR ₁ group and -CONH- group are ortho-positioned to each other, -COOR ₂ group and -CO- group are mutually ortho-positioned. 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 at least one of _{R 1} and R ₂ This is group represented by said 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 method according to claim 1 or 2,
The component (D) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-(4 -Methylphenylimino) at least one photosensitive resin composition selected from the group consisting of diethanol. 3. The method according to claim 1 or 2,
The photosensitive resin composition in which the said (D)component contains the compound represented by following formula (17).

(In formula (17), R _31A to R _33A are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxyl group, or a monovalent aromatic group, and among R _31A to R _33A At least one is a monovalent aromatic group. R _31A to R _33A may form a ring between adjacent groups.) 5. The method according to any one of claims 1 to 4,
The photosensitive resin composition in which the said (C)component contains the compound represented by (C1) following formula (15), and (C2) the compound represented by following formula (16).

(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 are each independently represents a hydrogen atom, an alkyl group having 1 to 12 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.)

(In formula (16), R _21A is an alkyl group having 1 to 12 carbon atoms, R _22A and R _23A are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 4 to 10 carbon atoms of a cycloalkyl group, a phenyl group, or a tolyl group, and 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, respectively.) 6. The method according to any one of claims 1 to 5,
The photosensitive resin composition in which the said (B) component contains the polymerizable monomer which has aliphatic cyclic skeleton. 7. The method according to any one of claims 1 to 6,
The photosensitive resin composition in which the said (B) component has group containing a polymerizable unsaturated double bond. 8. The method of claim 7,
The photosensitive resin composition whose said (B) component is a polymerizable monomer which has group containing two or more polymerizable unsaturated double bonds. 8. The method according to any one of claims 1 to 7,
The photosensitive resin composition in which the said (B) component contains the polymerizable monomer represented by 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 It is an integer, and n1+n2 is equal to or greater than 1. At least one of n1 pieces of R ₆ and n2 pieces of R ₇ is a group 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 l is an integer of 0 to 10.) 10. The method of claim 9,
The photosensitive resin composition whose n1+n2 is 2 or 3. 11. The method according to any one of claims 1 to 10,
The photosensitive resin composition in which the said (B) component contains the polymerizable monomer represented by following formula (5).

12. The method according to any one of claims 1 to 11,
(F) The photosensitive resin composition further comprising a thermal polymerization initiator. 13. The method according to any one of claims 1 to 12,
The photosensitive resin composition further containing antioxidant. The process of apply|coating and drying the photosensitive resin composition in any one of Claims 1-13 on a board|substrate to form a photosensitive resin film;
a step of pattern exposing the photosensitive resin film to obtain a resin film;
A step of developing the resin film after the pattern exposure using an organic solvent to obtain a pattern resin film;
The manufacturing method of the pattern hardened|cured material including the process of heat-processing the said pattern resin film. 15. The method of claim 14,
The manufacturing method of the pattern hardened|cured material whose said heat processing temperature is 230 degrees C or less. Hardened|cured material which hardened|cured the photosensitive resin composition in any one of Claims 1-13. 17. The method of claim 16,
A cured product that is a pattern cured product. An interlayer insulating film, a cover coat layer, or a surface protective film produced using the cured product according to claim 16 or 17. An electronic component comprising the interlayer insulating film according to claim 18, a cover coat layer, or a surface protective film.

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