KR20210068419A - 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) Polyimide precursor, (B) polymerizable monomer, (C) photoinitiator, (D) rust preventive agent, (E) antioxidant, (F) cyclization catalyst, and (G) photosensitive resin composition containing 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. have.

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, the composition containing a polyimide precursor is disclosed as a resin composition or a photosensitive composition (for example, refer patent documents 3 and 4).

Patent Document 1: Japanese Patent Laid-Open No. 2009-265520 Patent Document 2: International Publication No. 2008/111470 Patent Document 3: Japanese Patent Application Laid-Open No. 62-127840 Patent Document 4: Japanese Patent Laid-Open No. 2016-199662

An object of the present invention is to form a cured product having excellent insulation reliability, adhesion and migration even at low temperature curing of 230° C. or less, and a photosensitive resin composition having excellent sensitivity, 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 are provided.

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

1. (A) a polyimide precursor,

(B) a polymerizable monomer;

(C) a photoinitiator;

(D) a rust inhibitor;

(E) antioxidants;

(F) a cyclization catalyst, and

(G) solvent

A photosensitive resin composition containing.

2. The photosensitive resin composition according to 1, wherein the component (A) has a polymerizable unsaturated bond.

3. The photosensitive resin composition as described in 1 or 2 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.)

4. The photosensitive resin composition in any one of 1-3 in which said (B) component contains the polymerizable monomer which has aliphatic cyclic skeleton.

5. The photosensitive resin composition in any one of 1-4 in which the said (B) component has group containing a polymerizable unsaturated double bond.

6. The photosensitive resin composition according to 5, wherein the component (B) is a polymerizable monomer having a group containing two or more polymerizable unsaturated double bonds.

7. The photosensitive resin composition in any one of 1-5 in which 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 greater than or equal to 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.)

8. The photosensitive resin composition of 7 whose n1+n2 is 2 or 3.

9. The photosensitive resin composition in any one of 1-8 in which said (B) component contains the polymerizable monomer represented by following formula (5).

10. The component (F) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2' -(4-methylphenylimino) The photosensitive resin composition in any one of 1-9 chosen from the group which consists of diethanol.

11. The photosensitive resin composition in any one of 1-9 in which said (F) 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.)

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

13. The process of apply|coating and drying the photosensitive resin composition in any one of 1-12 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.

14. The manufacturing method of the pattern hardened|cured material of 13 whose said heat processing temperature is 230 degrees C or less.

15. Hardened|cured material which hardened the photosensitive resin composition in any one of 1-12.

16. The cured product according to 15, which is a pattern cured product.

17. An interlayer insulating film, cover coat layer, or surface protective film produced using the cured product according to 15 or 16.

18. An electronic component comprising the interlayer insulating film, cover coat layer, or surface protective film according to 17.

According to the present invention, it is possible to form a cured product excellent in insulation reliability, adhesiveness and migration even at low temperature curing of 230° C. or less, and a photosensitive resin composition excellent in sensitivity, a method for producing a pattern cured product, a cured product, an interlayer insulating film, a cover A coating layer, a surface protective film, and an electronic component can 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 this invention is (A) polyimide precursor (henceforth "(A) component"), (B) polymerizable monomer (it is also referred to as "(B) component" hereafter), (C) ) photoinitiator (hereinafter also referred to as “component (C)”), (D) rust inhibitor (hereinafter also referred to as “component (D)”), (E) antioxidant (hereinafter also referred to as “component (E)”) ), (F) a cyclization catalyst (hereinafter, also referred to as “component (F)”), and (G) a solvent (hereinafter also referred to as “component (G)”).

Thereby, even if it is low temperature hardening of 230 degreeC or less, it can form the hardened|cured material excellent in insulation reliability, adhesiveness, and migration, and it is excellent in sensitivity.

As an arbitrary effect, even if it is a case where the wiring width is extremely fine 2 micrometers or less, the hardened|cured material which can maintain the outstanding insulation and can suppress peeling from an electrode and Cu migration can be formed.

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.

It is preferable that the photosensitive resin composition of this invention is for fine Cu wiring patterns of 2 micrometers width and 2 micrometers space|interval.

Moreover, it is preferable that the photosensitive resin composition of this invention is for WLP (wafer-level package) whose number of input/output pins is several thousand (currently, the number of input/output pins is several hundred).

Moreover, it is preferable that the photosensitive resin composition of this invention is for devices which integrated the device divided into two or more chips into one chip. Thereby, it becomes possible to provide a highly space-saving, lightweight and highly functional package.

Moreover, it is preferable that the photosensitive resin composition of this invention is for devices, such as a smart watch, smart glasses, a smart contact lens, a nano drone.

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.

It is preferable that (A) component has a polymerizable unsaturated bond from a viewpoint of a photosensitive improvement.

As a polymerizable unsaturated bond, a carbon-carbon double bond 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, and m is an integer of 1 to 10 (preferably an integer of 2 to 5, more preferably It is usually 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.

The component (B) is a group containing a polymerizable unsaturated double bond (preferably two or more) from the viewpoint of improving the hydrophobicity of the cured product (preferably, from the viewpoint of being polymerizable with a photoinitiator, (meth) acrylic group). 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.

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.

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, etc. can be heard

Tetraethylene glycol dimethacrylate is preferred.

(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 achieving both the mechanical strength and hydrophobicity improvement of the cured product.

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.

By including (D) component, corrosion suppression and discoloration of copper and a copper alloy can be prevented.

(D) As a component, a triazole derivative, a tetrazole derivative, etc. are mentioned, for example.

(D) As a component, 5-aminotetrazole (for example, 5-amino-1H-tetrazole), benzotriazole, 1-hydroxybenzotriazole, 1H-benzotriazole-1-acetonitrile, benzo and triazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and mercaptobenzoxazole. Among these, 5-aminotetrazole, benzotriazole, or 1-hydroxybenzotriazole is preferable.

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

(D) 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component, as for content of component, 0.1-5 mass parts is more preferable, 0.5-3 mass parts is still more preferable.

By containing the component (E), oxygen radicals and peroxide radicals generated during high-temperature storage or insulation reliability tests are supplemented, and a decrease in adhesiveness (adhesiveness) can be further suppressed.

(E) As a component, 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.

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

(E) 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.

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

(F) component is 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N from a viewpoint of a cyclization rate and a sensitivity improvement ,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-(4-methylphenylimino)diethanol is preferably at least one selected from the group consisting of, N-phenyldiethanol From the group consisting of amine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-(4-methylphenylimino)diethanol It is more preferable that it is 1 or more chosen.

(F) 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 1 or 2) is a monovalent aromatic _{group.R 31A} to R _33A represent a 5-membered ring which may have a substituent (for example, a methyl group or a phenyl group) between adjacent groups. Or a 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} the 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.

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

As for content of (F) component, 0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component from a viewpoint of fully trapping oxygen radicals. From a viewpoint of suppressing a glass transition temperature (Tg) fall, 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 (G) a solvent.

(G) 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, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, 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, you may use the compound represented by following formula (21) as (G)component.

(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)).

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

Although content of (G) 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 (H) thermal-polymerization initiator (henceforth "(H) component".) from a viewpoint of polymerization reaction acceleration|stimulation.

As the component (H), 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, or (A) component and ( B) A compound that promotes the polymerization reaction of the component is preferred.

The decomposition point of the component (H) is preferably a compound of 110°C or more and 200°C or less, and more preferably a compound of 110°C or more and 175°C or less from the viewpoint of accelerating the polymerization reaction at a lower temperature.

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-mentane hydroperoxide Hydroperoxide such as dicumyl peroxide, dialkyl peroxide such as di-t-butyl peroxide, diacyl peroxide such as dilauroyl peroxide and dibenzoyl peroxide, di(4-t-butylcyclohexyl) Peroxydicarbonate such as peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate and peroxyesters such as , 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and bis(1-phenyl-1-methylethyl)peroxide. As a commercial item, "Percumyl D", "Percumyl P", "Percumyl H" (above, Nichiyu Corporation make), etc. are mentioned as a commercial item.

When the component (H) is contained, the content of the component (H) 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 contain a coupling agent (adhesion auxiliary agent), surfactant, or a leveling 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, 1-10 mass parts is more preferable, 0.3-10 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 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 (G), and optionally component (H), a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor, and does not impair the effects of the present invention. Other unavoidable impurities may be included to the extent that the

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 (G) components,

(A) to (H) components, or

(A) - (G) component, and optionally (H) component, a coupling agent, surfactant, a leveling agent, and a polymerization inhibitor may consist of it.

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, ultraviolet rays such as i-rays, visible rays, and radiation, and is preferably i-rays.

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 160-230 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 1-3

(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 1-3 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: TGDMA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., tetraethylene glycol dimethacrylate)

(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: Rust inhibitor

D1: 5-amino-1H-tetrazole (manufactured by Tokyo Kasei Industrial Co., Ltd.)

(E) Ingredient: Antioxidant

E1: ANTAGE HP200 (manufactured by Kawaguchi Chemical Industry Co., Ltd., N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethylcarbonyloxy]ethyl]oxamide; A compound represented by the following formula E1)

E2: ANTAGE HP300 (manufactured by Kawaguchi Chemical Industry Co., Ltd., N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, a compound represented by the following formula E2 )

E3: THTT (manufactured by Combi-Blocks, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4, 6-(1H,3H,5H)-trione, a compound represented by the following formula E3)

(F) component: cyclization catalyst

F1: 2HE (manufactured by Morin Chemical Industry Co., Ltd., N-phenyldiethanolamine)

(G) Component: Solvent

G1: KJCMPA-100 (manufactured by KJ Chemicals, a compound represented by the following formula G1)

(H) component: thermal polymerization initiator

H1: Percumyl D (manufactured by Nichiyu Corporation, bis(1-phenyl-1-methylethyl)peroxide, a compound represented by the following formula)

(Evaluation of sensitivity)

The obtained photosensitive resin composition was spin-coated on a silicon wafer using the coating device Act8 (manufactured by Tokyo Electron Corporation), dried at 100°C for 2 minutes, dried at 110°C for 2 minutes, and a dry film thickness of 11 to 14 µm A phosphorus photosensitive 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 an i-line stepper FPA-3000iW (manufactured by Canon Corporation) was used to the obtained photosensitive resin film, and an i-line of 50 to 550 mJ/cm 2 was applied at 50 mJ/cm 2 increments. It was irradiated in a predetermined pattern with an irradiation amount, and exposure was performed.

The resin film after exposure was paddle-developed in cyclopentanone for the said development time using Act8, Then, rinse washing was performed with propylene glycol monomethyl ether acetate (PGMEA), and the pattern resin film was obtained.

The lower limit of the exposure amount at which the film thickness of the obtained patterned resin film became more than 75% of the film thickness of the photosensitive resin film before exposure was made into sensitivity. The film thickness was measured using a folding profiler Dektak150 (manufactured by Bruker), exposing a silicon wafer by chasing a portion of the film and measuring the height from the exposed silicon wafer surface to the film surface (film thickness). The measurement of thickness is the same hereafter).

A case where the sensitivity was less than 300 mJ/cm 2 was designated as A. The case of 300-400 mJ/cm<2> was made into B. The case where it exceeded 300 mJ/cm<2> was made into C. A result is shown in Table 1.

(Manufacture of pattern cured product)

The pattern resin film obtained in the sensitivity evaluation was heated for 1 hour at 200°C in a nitrogen atmosphere using µ-TF (manufactured by Koyo Thermosystems Co., Ltd.) in a vertical diffusion furnace to obtain a pattern cured product (film thickness 10 µm after curing). got it

About Examples 1-3, favorable pattern hardened|cured material was obtained.

<Evaluation of insulation reliability>

Test substrate for biasHAST (high-speed accelerated life test) (silicon wafer/SiO ₂ layer (1 μm)/TiCu seed layer (100 nm)/Cu layer (3.5 μm) layer configuration wafer, silicon wafer/SiO ₂ layer/TiCu A wafer with a layer configuration called a seed layer is manufactured by Advanced Material Technology Co., Ltd., and the TiCu seed layer and Cu layer have a comb pattern (comb line width: 2 μm, number of teeth: 9 anodes, 9 cathodes, spacing: 2 μm) ) was used.

The obtained photosensitive resin composition was spin-coated on the test board|substrate for biasHAST, and it dried at 120 degreeC for 3 minutes, and after drying, the photosensitive resin film with a film thickness of 10 micrometers was formed. In addition, the surface of the test board|substrate for biasHAST had a pad part, and application|coating was performed so that the photosensitive resin composition might not be apply|coated to a pad part.

The obtained photosensitive resin film was heated at 200 degreeC in nitrogen atmosphere using micro-TF for 1 hour, and the test board|substrate with hardened|cured material (film thickness 8 micrometers after hardening) adhered was obtained. Thereafter, the pad portion of the test board with the cured product was soldered, connected to a migration tester MIG-8600B (manufactured by IMV Co., Ltd.), and heated to a constant temperature chamber HASTEST PC-R8D (manufactured by Hirayama Corporation) at 130° C., 85 %RH (relative humidity), DC (Direct Current): It was input under the conditions of 3.3V, and conduction|electrical_connection was confirmed up to 300 hours.

The thing in which the short circuit of a circuit did not arise from the start of a test to 300 hours was made into A. What a short circuit of a circuit occurred in more than 100 hours and less than 300 hours from the start of a test was made into B. What a short circuit of a circuit occurred within 100 hours from the start of a test was set as C. A result is shown in Table 1.

< Cu adhesion evaluation >

About the test board|substrate with hardened|cured material after the said insulation reliability evaluation, cross-sectional observation was performed using the scanning electron microscope (SEM) IM4000 (made by Hitachi High-Technologies Corporation). At the interface of Cu layer and hardened|cured material, the thing in which peeling was not seen was made into A. The thing in which peeling of less than 0.2 micrometer was seen was made into B. The thing in which peeling of 0.2 micrometer or more was seen was designated as C. A result is shown in Table 1.

<Cu migration evaluation>

SEM-EDX (energy dispersive X-ray spectroscopy) analysis using a Schottky field emission scanning electron microscope JSM-7800F-prime (manufactured by Nippon Electronics Co.) was carried out. A case in which diffusion of Cu was not detected between the cathode and the anode of the comb-tooth pattern was designated as A. A case in which diffusion of Cu was detected in a range of less than 0.5 µm from the electrode was designated as B. Cu diffusion was detected in a range of 0.5 µm or more from the electrode was designated as C. A result is shown in Table 1.

Specifically, Pt sputtering was carried out on the test board|substrate with hardened|cured material after the said insulation reliability evaluation, and it arrange|positioned in JSM-7800F-prime. It was measured over 1 hour under the condition of current value: beam 16 (2.7 nA) with an acceleration voltage of 2 kV.

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 (18)

(A) a polyimide precursor,
(B) a polymerizable monomer;
(C) a photoinitiator;
(D) a rust inhibitor;
(E) antioxidants;
(F) a cyclization catalyst, and
(G) solvent
A photosensitive resin composition containing. The method of claim 1,
The photosensitive resin composition in which the said (A) component has a polymerizable unsaturated bond. 3. The method according to claim 1 or 2,
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.) 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition in which the said (B) component contains the polymerizable monomer which has an aliphatic cyclic skeleton. 5. The method according to any one of claims 1 to 4,
The photosensitive resin composition in which the said (B) component has group containing a polymerizable unsaturated double bond. 6. The method of claim 5,
The photosensitive resin composition whose said (B) component is a polymerizable monomer which has group containing two or more polymerizable unsaturated double bonds. 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 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.) 8. The method of claim 7,
The photosensitive resin composition whose n1+n2 is 2 or 3. 9. The method according to any one of claims 1 to 8,
The photosensitive resin composition in which the said (B) component contains the polymerizable monomer represented by following formula (5).

10. The method according to any one of claims 1 to 9,
The component (F) is N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-( At least one photosensitive resin composition selected from the group consisting of 4-methylphenylimino)diethanol. 10. The method according to any one of claims 1 to 9,
The photosensitive resin composition in which the said (F) 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.) 12. The method according to any one of claims 1 to 11,
(H) The photosensitive resin composition further comprising a thermal polymerization initiator. The process of apply|coating and drying the photosensitive resin composition in any one of Claims 1-12 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. 14. The method of claim 13,
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 1-12. 16. The method of claim 15,
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 15 or 16. An electronic component comprising the interlayer insulating film according to claim 17, a cover coat layer, or a surface protective film.

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