JP2022154451A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition or the like that can give a cured product having excellent limiting resolution and dielectric properties.SOLUTION: A photosensitive resin composition contains (A) a polyimide precursor, (B) a crosslinker, (C) a photoradical generator, and (D) at least one resin selected from the group consisting of an indene resin and a coumarone-indene resin.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin composition. Furthermore, the present invention relates to a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for producing a semiconductor package substrate obtained using the photosensitive resin composition.

BACKGROUND ART Conventionally, polyimide resins, which are excellent in heat resistance and insulation properties, have been used for insulating layers of semiconductor devices. Further, since the polyimide resin has low solubility in solvents, in the photosensitive resin composition, it is used in the form of a polyimide precursor, and after forming an insulating layer or the like, the polyimide precursor is cyclized to form an insulating layer. (See Patent Document 1, for example).

JP-A-2003-084435

In recent years, with the increase in communication speed and capacity in communication equipment, the photosensitive resin composition used for the semiconductor package substrate of communication equipment has excellent resolution, and the dielectric constant and dielectric loss tangent of the cured product are low. Therefore, excellent dielectric properties have been demanded.

The present invention has been made in view of the above problems, a photosensitive resin composition excellent in limiting resolution and dielectric properties of the cured product, a photosensitive film obtained using the photosensitive resin composition, a semiconductor An object of the present invention is to provide a package substrate, a semiconductor device, and a method of manufacturing a semiconductor package substrate.

As a result of intensive studies by the present inventors, the photosensitive resin composition contains a polyimide precursor, a cross-linking agent, a photoradical generator, and at least one resin selected from the group consisting of an indene resin and a coumarone-indene resin. The present inventors have found that the above problems can be achieved by this, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) a polyimide precursor,
(B) a cross-linking agent;
(C) a photoradical generator, and (D) at least one resin selected from the group consisting of indene resins and coumarone-indene resins,
A photosensitive resin composition containing
[2] The photosensitive resin composition according to [1], further comprising (E) a sensitizer.
[3] The photosensitizer according to [1] or [2], wherein the content of component (D) is 1% by mass or more and 10% by mass or less when the nonvolatile component of the photosensitive resin composition is 100% by mass. elastic resin composition.
[4] Any one of [1] to [3], wherein the content of component (A) is 70% by mass or more and 98% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. The photosensitive resin composition described.
[5] A photosensitive film comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [4] formed on the support.
[6] A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [4].
[7] A semiconductor device including the semiconductor package substrate according to [6].
[8] forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [4] on a circuit board;
A step of irradiating the photosensitive resin composition layer with an actinic ray;
and a step of developing the photosensitive resin composition layer.

INDUSTRIAL APPLICABILITY According to the present invention, a photosensitive resin composition excellent in limited resolution and dielectric properties of a cured product, a photosensitive film, a semiconductor package substrate, a semiconductor device, and a semiconductor package obtained by using the photosensitive resin composition A method of manufacturing a substrate can be provided.

The photosensitive resin composition, the photosensitive film, the semiconductor package substrate, the semiconductor device, and the method for producing the semiconductor package substrate of the present invention are described in detail below. In the following description, "permittivity" means "relative permittivity" unless otherwise specified.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention includes (A) a polyimide precursor, (B) a cross-linking agent, (C) a photoradical generator, and (D) at least one selected from the group consisting of an indene resin and a coumarone-indene resin. Contains seed resin. By incorporating the components (A) to (D) in combination into the photosensitive resin composition, a cured product excellent in limited resolution and dielectric properties can be obtained.

The photosensitive resin composition of the present invention is suitable as a negative photosensitive resin composition.

The photosensitive resin composition may further contain optional components in combination with components (A) to (D). Examples of optional components include (E) a sensitizer, (F) other additives, and (G) a solvent. Each component contained in the photosensitive resin composition will be described in detail below.

<(A) polyimide precursor>
The photosensitive resin composition contains (A) a polyimide precursor as the (A) component. By including the component (A) in the photosensitive resin composition, it is possible to obtain a cured product having excellent marginal resolution and excellent dielectric properties. (A) Component may be used individually by 1 type, and may be used in combination of 2 or more type.

（式中、Ａはそれぞれ独立に４価の有機基を表し、Ｂはそれぞれ独立に置換基を有していてもよい２価の有機基を表し、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子又は１価の有機基を表す。ｎは５～２００の整数を表す。） A resin having a plurality of amic acid structures and/or amic acid ester structures can be used as component (A). The component (A) preferably has a structural unit represented by the following formula (A-1) from the viewpoint of obtaining a cured product with excellent resolution limit and excellent dielectric properties.

(Wherein, A each independently represents a tetravalent organic group, B each independently represents a divalent organic group which may have a substituent, R ¹ and R ² each independently represent a hydrogen represents an atom or a monovalent organic group. n represents an integer of 5 to 200.)

In formula (A-1), each A independently represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group having 6 to 40 carbon atoms is preferred. Examples of the tetravalent organic group having 6 to 40 carbon atoms include an aromatic group in which -COOR ¹ group and -COOR ² group and -CONH- group in formula (A-1) are ortho to each other, or an alicyclic aliphatic group. Such groups include, for example, groups (i) to (ix). Also, a group obtained by combining two or more of the groups (i) to (ix) may be used. Among them, A is preferably a tetravalent organic group exemplified below, and more preferably group (viii) or group (ix). In the formula, * represents a bond.

In formula (A-1), each B independently represents a divalent organic group. The divalent organic group preferably has an aromatic ring. Examples of divalent organic groups include groups (1a) to (19a) shown below. Further, it may be a group in which two or more of the groups (1a) to (19a) are combined. B is preferably the group (2a) or the group (19a). In the formula, * represents a bond.

The divalent organic group may have a substituent. Examples of substituents include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, and n-butyl; fluorine, chlorine, and bromine atoms. alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group and propoxy group; hydroxy group; halogen atom-substituted alkyl groups such as trifluoromethyl group and the like, and alkyl groups are preferred. The substituents described above may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituents may be contained singly or in combination of two or more.

（式中、Ｒ^４～Ｒ^６は、それぞれ独立に、水素原子又は炭素原子数１～３の脂肪族炭化水素基を表し、ｐは１～１０の整数を表す。） R ¹ and R ² in formula (A-1) each independently represent a hydrogen atom or a monovalent organic group. Examples of monovalent organic groups include saturated aliphatic groups having 1 to 4 carbon atoms; reactive groups that can be polymerized by radicals generated by heat or light, namely radical reactive groups, and the like, which are radical reactive groups. is preferred. Preferably, at least one of R ¹ and R ² in formula (A-1) is independently a radical reactive group, more preferably both are radical reactive groups. As the radical reactive group, a group represented by the following formula (A-2) is preferable.

(In the formula, R ⁴ to R ⁶ each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.)

R ⁴ to R ⁶ in formula (A-2) each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of aliphatic hydrocarbon groups having 1 to 3 carbon atoms include alkyl groups having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms includes, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, etc. Among them, methyl group is preferred.

The saturated aliphatic group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group and the like. mentioned.

p in formula (A-2) represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 2.

At least one of R ¹ and R ² in formula (A-1) is each independently preferably a radical reactive group, more preferably at least one is a group represented by formula (A-2). More preferably, both R ¹ and R ² are groups represented by formula (A-2).

n in formula (A-1) represents an integer of 5-200, preferably an integer of 5-150, more preferably an integer of 5-100, and still more preferably an integer of 5-70.

Specific examples of component (A) include the following compounds (A1) to (A2). However, the component (A) is not limited to these specific examples. In the formula, n represents an integer of 5-200.

The weight-average molecular weight of component (A) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, and preferably 1,000,000 or less, more preferably, from the viewpoint of significantly obtaining the effects of the present invention. It is 500,000 or less, more preferably 200,000 or less. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by a gel permeation chromatography (GPC) method.

(A) There are no particular restrictions on the method for producing the component. The component (A) can usually be obtained by reacting a tetracarboxylic dianhydride and a diamine compound. Component (A) can be produced by the method described in, for example, JP-A-2015-209461, JP-A-2015-214680, JP-A-2017-219850, or JP-A-2018-146964. .

The content of component (A) is preferably 10% by mass or more, more preferably 20% by mass, based on 100% by mass of non-volatile components in the photosensitive resin composition, from the viewpoint of significantly obtaining the effects of the present invention. Above, more preferably 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, preferably 99% by mass or less, more preferably 95% by mass or less, and further Preferably, it is 90% by mass or less. In the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile component in the photosensitive resin composition is 100% by mass, unless otherwise specified.

<(B) Crosslinking agent>
The photosensitive resin composition contains (B) a cross-linking agent as the (B) component. However, the (B) component excludes those corresponding to the (A) component. When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from the photo-radical generator, the component (B) undergoes a cross-linking reaction or the like and becomes insoluble in the developer. Therefore, during development, the photosensitive resin composition can be selectively removed in areas other than the areas where the cross-linking reaction has progressed, and a negative pattern can be advantageously formed. (B) component may be used individually by 1 type, and may be used in combination of 2 or more type.

As the component (B), a compound capable of promoting a cross-linking reaction during development can be used. Such a compound is preferably a compound having an ethylenically unsaturated bond, further has an ethylenically unsaturated bond, and at least one of the α-position carbon atoms of the ethylenically unsaturated bond is a carbonyl group or an aromatic More preferred are compounds attached to a group group. The carbon atom at the α-position of the ethylenically unsaturated bond indicates the first carbon atom adjacent to the carbon atom bonded by the carbon-carbon double bond.

Ethylenically unsaturated bonds represent carbon-carbon double bonds. Therefore, the component (B) may contain a group having an ethylenically unsaturated bond (hereinafter sometimes referred to as an "ethylenically unsaturated group"). The ethylenically unsaturated group is usually a monovalent group, examples of which include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, and (meth)acryloyl group. From the viewpoint of photoradical polymerization reactivity, a (meth)acryloyl group and a phenylethynyl group are preferred, and a (meth)acryloyl group is particularly preferred. A "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. Since component (B) contains an ethylenically unsaturated bond, photoradical polymerization is possible. However, in performing photoradical polymerization under general conditions, at least one Compounds having a carbonyl group or an aromatic group in are preferred. The number of ethylenically unsaturated bonds per molecule of component (B) is preferably 1 or more, more preferably 2 or more. Moreover, when the component (B) contains two or more ethylenically unsaturated groups per molecule, those ethylenically unsaturated groups may be the same or different.

（式中、Ｒ^１ｂは、それぞれ独立に、水素原子、又は炭素原子数１～４の直鎖状もしくは分岐状アルキル基を表し、Ｚ^１ｂは、それぞれ独立に、酸素原子を含んでもよい炭素原子数１～２０の直鎖状もしくは分岐状のアルキレン基、酸素原子を含んでもよいアリーレン基、又は酸素原子を含んでもよい炭素原子数２～２０の直鎖状もしくは分岐状のアルケニレン基を表し、Ａ^１ｂは、炭素原子数１～１０の直鎖状、環状もしくは分岐状のｎｂ価の有機基を表す。ｎｂは２～６の正の整数を示す。） As the component (B), a compound represented by the following general formula (B-1) is preferable.

(wherein each R ^1b independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; each Z ^1b independently represents a carbon atom which may contain an oxygen atom; represents a linear or branched alkylene group of number 1 to 20, an arylene group which may contain an oxygen atom, or a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, A ^1b represents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms, where nb is a positive integer of 2 to 6.)

Each R ^1b independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of linear or branched alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, s-butyl group and t-butyl group. be done. Among them, R ^1b is preferably a hydrogen atom or a methyl group.

Z ^1b is each independently a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, an arylene group which may contain an oxygen atom, or the number of carbon atoms which may contain an oxygen atom It represents 2 to 20 linear or branched alkenylene groups. The linear or branched alkylene group having 1 to 20 carbon atoms is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 1 to 6 carbon atoms. A triangular alkylene group is more preferred. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like, and a methylene group is preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include the following. In the formula, "*" represents a bond, and a represents an integer of 1-23.

As the arylene group which may contain an oxygen atom, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 15 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is even more preferable. Examples of such an arylene group include a phenylene group and a naphthylene group. In addition, the arylene group may contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1-23.

The linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom is preferably a linear or branched alkenylene group having 2 to 10 carbon atoms, and 2 to 6 carbon atoms. A linear or branched alkenylene group of is more preferable. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene groups. Also, the alkenylene group may be an oxyalkenylene group containing an oxygen atom, and specific examples of such groups include the following. In the formula, "*" represents a bond, and a represents an integer of 1-23. A propenylene group is preferred as the alkenylene group.

Among them, Z ^1b is preferably a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, more preferably a methylene group.

A ^1b represents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms. Examples of nb-valent organic groups include nb-valent hydrocarbon groups that may contain an oxygen atom, nb-valent groups derived from bisphenol, nb-valent groups derived from fluorene, and nb-valent groups derived from tricyclodecane. , or an nb-valent group derived from an isocyanuric group. Examples of the nb-valent hydrocarbon group which may contain an oxygen atom include nb-valent aliphatic hydrocarbon groups which may contain an oxygen atom and nb-valent aromatic hydrocarbon groups which may contain an oxygen atom. An nb-valent aliphatic hydrocarbon group which may contain is preferred. Specific examples of the group represented by A ^1b include those shown below. In the formula, "*" represents a bond.

nb represents a positive integer of 2 to 6, preferably a positive integer of 2 to 5, more preferably an integer of 2 to 4, and 2 or 3;

（式中、Ｒ^２ｂは、それぞれ独立に水素原子、又はメチル基を表す。） As the component (B), a compound represented by the following general formula (B-2) is preferable.

(In the formula, each R ^2b independently represents a hydrogen atom or a methyl group.)

R ^2b represents a hydrogen atom or a methyl group, preferably a methyl group.

Specific examples of component (B) include the following compounds (CL-1) to (CL-11). However, the (B) component is not limited to these.

(B) A commercial item can be used for a component. Commercially available products include, for example, NK Ester-D-TMP, 4G, 9G, 14G, 23G and DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

The content of component (B) is preferably 0.1% by mass or more, more preferably 0% by mass, when the non-volatile component of the photosensitive resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. .5% by mass or more, more preferably 1% by mass or more, 2% by mass or more, 3% by mass or more, preferably 20% by mass or less, more preferably 18% by mass or less, further preferably 15% by mass or less .

<(C) Photoradical Generator>
The photosensitive resin composition contains (C) a photoradical generator. The component (C) is irradiated with actinic rays to generate radicals, and the radicals can cause a cross-linking reaction to proceed. In the photosensitive resin composition, the portion where the cross-linking reaction is caused by the radicals is cured to become a cured product, and the resistance to the developing solution is improved. Therefore, during development, the photosensitive resin composition can be selectively removed in areas other than the areas where the cross-linking reaction has progressed, and a negative pattern can be advantageously formed. (C) component may be used individually by 1 type, and may be used in combination of 2 or more type. Components (A) to (B) are excluded from the (C) component.

Component (C) includes benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, benzophenone derivatives such as fluorenone, 2,2′-diethoxyacetophenone, 2-hydroxy- Acetophenone derivatives such as 2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; benzyl, benzyl dimethyl ketal, benzyl-β-methoxyethyl acetal benzyl derivatives such as; benzoin, benzoin methyl ether and other benzoin derivatives; -methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, 1,3 -oximes such as diphenylpropanetrione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(o-benzoyl)oxime; N-arylglycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octane sulfonyloxyimino)-4-methoxybenzyl cyanide; Among them, oximes are preferable as the component (C) from the viewpoint of photosensitivity.

(C) A commercial item can be used for a component. Examples of commercially available products include "Irgacure-OXE02" and "Irgacure-OXE04" manufactured by BASF.

The content of component (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of component (A), from the viewpoint of significantly obtaining the effects of the present invention. , more preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 17 parts by mass or less, still more preferably 15 parts by mass or less.

The content of component (C) is preferably 0.1% by mass or more, more preferably 0.1% by mass or more, when the non-volatile component of the photosensitive resin composition is 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. It is 0.5% by mass or more, more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

<(D) At least one resin selected from the group consisting of indene resins and coumarone-indene resins>
The photosensitive resin composition contains, as component (D), at least one resin selected from the group consisting of (D) indene resins and coumarone-indene resins. By including the component (D) in the photosensitive resin composition, it is possible to obtain a cured product having excellent marginal resolution and excellent dielectric properties. (D) Component may be used individually by 1 type, and may be used in combination of 2 or more type. Components corresponding to the above-described components (A) to (C) are excluded from the component (D).

Indene resin refers to a polymer of monomers containing indene or alkylindene as an essential monomer. Indene resins are copolymers of essential monomers such as indene and alkylindene, and optional monomers such as styrene derivatives such as styrene and alkylstyrene, and phenol derivatives such as di-t-butylhydroxybenzene. may
Coumaron-indene resins refer to polymers of monomers containing indene or alkylindene as essential monomers, as well as coumarone. Chroman-indene resins are composed of essential monomers such as indene or alkylindene, and coumarone, and optional monomers such as styrene derivatives such as styrene and alkylstyrenes, and phenol derivatives such as di-t-butylhydroxybenzene. It may be a copolymer.
Component (D) is at least one selected from the group consisting of indene resins and coumarone-indene resins, preferably coumarone-indene resins. The coumarone-indene resin is preferably a copolymer of indene and coumarone, a copolymer of indene, coumarone and a styrene derivative, more preferably a copolymer of indene, coumarone and a styrene derivative.

The content ratio of the coumarone component in the coumarone-indene resin is preferably 5 mol % or more, more preferably 8 mol % or more, still more preferably 10 mol % or more. The upper limit is preferably 40 mol % or less, more preferably 35 mol % or less, still more preferably 30 mol % or less. A chroman component represents a repeating unit formed by polymerizing chroman.

The content ratio of the indene component in the coumarone-indene resin is preferably 30 mol % or more, more preferably 35 mol % or more, and still more preferably 40 mol % or more. The upper limit is preferably 80 mol % or less, more preferably 75 mol % or less, still more preferably 70 mol % or less. The indene component represents a repeating unit formed by polymerizing indene or alkylindene.

When the coumarone-indene resin is a copolymer of indene, coumarone and a styrene derivative, the content of the styrene derivative component is preferably 20 mol% or more, more preferably 25 mol% or more, and still more preferably 30 mol% or more. be. The upper limit is preferably 70 mol % or less, more preferably 65 mol % or less, still more preferably 60 mol % or less. A styrene derivative component represents a repeating unit formed by polymerizing styrene or a styrene derivative.

The softening point of component (D) is preferably 90°C or higher, more preferably 100 to 180°C, and particularly preferably 120 to 180°C. The softening point of component (D) is a value measured by the method described in JIS K2207.

(D) A commercial item can also be used for a component. Commercially available products of component (D) include "Nit Resin Coumaron H-100", "Knit Resin Coumaron V-120S" and "Nit Resin Coumaron V-120" manufactured by Nichinuri Kagaku Co., Ltd.

The content of the component (D) is preferably 1% by mass or more, more preferably 1.3% by mass, based on 100% by mass of the non-volatile components of the photosensitive resin composition, from the viewpoint of significantly obtaining the effects of the present invention. % or more, more preferably 1.5 mass % or more, preferably 15 mass % or less, more preferably 12 mass % or less, still more preferably 10 mass % or less.

The content of component (A) when the non-volatile component of the photosensitive resin composition is 100% by mass is a1, and the content of component (D) when the non-volatile component of the photosensitive resin composition is 100% by mass is d1, a1/d1 is preferably 1 or more, more preferably 5 or more, still more preferably 8 or more, preferably 200 or less, more preferably 150, from the viewpoint of significantly obtaining the effects of the present invention. 100 or less, more preferably 100 or less.

<(E) Sensitizer>
The photosensitive resin composition may contain (E) a sensitizer as an optional component. By including (E) a sensitizer in the photosensitive resin composition, it is possible to improve the photosensitivity of the photosensitive resin composition. (E) component may be used individually by 1 type, and may be used in combination of 2 or more type. Components (E) exclude those corresponding to the above-described components (A) to (D).

The (E) component can use a compound capable of improving the photosensitivity of the photosensitive resin composition. Examples of such compounds include benzophenones such as Michler's ketone, 4,4′-bis(diethylamino)benzophenone, 4-morpholinobenzophenone; 2,5-bis(4′-diethylaminobenzal)cyclopentane, 2,6 - Cyclic alkanes such as bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; 4,4'-bis(dimethylamino)chalcone, 4, Chalcones such as 4′-bis(diethylamino) chalcone; Indanones such as p-dimethylaminocinnamylideneindanone and p-dimethylaminobenzylideneindanone; 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2 - Thiazoles such as (p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3- Acetones such as bis(4′-diethylaminobenzal)acetone; 3,3′-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin , 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin; N-phenyl-N'-ethylethanolamine, N- Amines such as phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate; 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylamino styryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, 1-p-hydroxy heterocyclic compounds such as phenyl-5-mercaptotetrazole; and styrenes such as 2-(p-dimethylaminobenzoyl)styrene.

（式（Ｅ－１）中、Ｒ^１ｅは、水素原子、炭素原子数１～７の直鎖状もしくは分岐状アルキル基、ハロゲン原子、ヒドロキシ基、メトキシ基、又はｔ－ブトキシ基を表す。） Among them, the component (E) is preferably a heterocyclic compound, more preferably a compound represented by the following general formula (E-1), from the viewpoint of significantly obtaining the effects of the present invention.

(In formula (E-1), R ^1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group.)

R ^1e represents a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, a halogen atom, a hydroxy group, a methoxy group, or a t-butoxy group. Examples of linear or branched alkyl groups having 1 to 7 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group and the like. Among them, R ^1e preferably represents a hydroxy group having an oxygen atom, a methoxy group, or a t-butoxy group, preferably a hydrogen atom or a hydroxy group, and more preferably a hydrogen atom.

The bonding position of R ^1e may be any of the ortho-, meta-, and para-positions with respect to the site of the phenylene group bonded to the nitrogen atom of mercaptotetrazole. From the viewpoint of obtaining, the para position is preferable.

The compound represented by (E-1) is preferably either a compound represented by (E-2) below or a compound represented by (E-3) below.

The content of component (E) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of component (A), from the viewpoint of significantly obtaining the effects of the present invention. It is more preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and even more preferably 15 parts by mass or less.

The content of the component (E) is preferably 0.1% by mass or more, more preferably 0.1% by mass, based on 100% by mass of non-volatile components in the photosensitive resin composition, from the viewpoint of obtaining the effects of the present invention remarkably. It is 5% by mass or more, more preferably 1% by mass or more, preferably 20% by mass or less, more preferably 17% by mass or less, and even more preferably 15% by mass or less.

<(F) Other additives>
The photosensitive resin composition may further contain (F) other additives to the extent that the object of the present invention is not impaired. (F) Other additives include, for example, adhesion aids; surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants ; Thermoplastic resins; Colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black; Polymerization inhibitors; thickeners such as bentone and montmorillonite; silicone-, fluorine-, and vinyl-resin-based defoaming agents; epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphates, halogen-containing condensed phosphates flame retardants such as; and thermosetting resins such as phenol-based curing agents and cyanate ester-based curing agents.

<(G) Solvent>
The photosensitive resin composition may contain (G) a solvent as an optional component in combination with the non-volatile components such as components (A) to (F) described above. The solvent (G) is a volatile component, and is preferably capable of uniformly dissolving at least one of components (A) to (D) and optional components (E) and (F). Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone; , and ketone compounds having 2 to 6 carbon atoms such as methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; and 3 or more carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate. Ester compounds with 9 or less carbon atoms; Halogen-containing compounds with 1 or more carbon atoms and 10 or less carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; Acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide , and nitrogen-containing compounds having 2 to 10 carbon atoms such as N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethylsulfoxide.

Examples of component (G) include N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoramide, pyridine, cyclopentanone, α-acetyl-γ-butyrolactone. , tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, anisole, ethyl acetate, ethyl lactate, and and butyl lactate. (G) Component may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of component (G) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 100% by mass of the entire photosensitive resin composition including component (G). It is 30% by mass or more, preferably 99% by mass or less, more preferably 97% by mass or less, and still more preferably 95% by mass or less. The content of the component (G) in the photosensitive resin composition layer of the photosensitive film is preferably 1% by mass or more when the entire photosensitive resin composition including the component (G) is taken as 100% by mass. , more preferably 2% by mass or more, still more preferably 3% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less be.

The photosensitive resin composition is prepared by mixing the above (A) to (D) components as essential components, and appropriately mixing the above (E) to (G) components as optional components. It can be produced by kneading or stirring with kneading means such as a ball mill, bead mill or sand mill, or stirring means such as a super mixer or planetary mixer.

<Physical properties and uses of the photosensitive resin composition>
The photosensitive resin composition exhibits a characteristic of being excellent in limited resolution. For example, exposure and development are performed using a mask for drawing round holes with opening diameters of exposure patterns of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably 25 μm or less, more preferably 20 μm or less, and even more preferably 15 μm or less. Evaluation of limiting resolution can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the photosensitive resin composition at 250° C. for 2 hours exhibits a characteristic of low dielectric constant (Dk). The dielectric constant at 23° C. is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less. Although the lower limit is not particularly limited, it may be 1 or more. The dielectric constant can be measured according to the method described in Examples below.

A cured product obtained by thermally curing the photosensitive resin composition at 250° C. for 2 hours exhibits a characteristic of low dielectric loss tangent (Df). The dielectric loss tangent at 23° C. is preferably 0.015 or less, more preferably 0.012 or less, still more preferably 0.09 or less. Although the lower limit is not particularly limited, it may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in Examples below.

Applications of the photosensitive resin composition of the present invention are not particularly limited, but include photosensitive films, insulating resin sheets such as prepreg, silicon wafers, circuit boards (laminated board applications, multilayer printed wiring board applications, etc.), solder resists, buffers It can be used in a wide range of applications where photosensitive resin compositions are used, such as coating films, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, and part-embedding resins. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of a photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition Printed wiring board with a cured product as an interlayer insulating layer), photosensitive resin composition for plating (printed wiring board in which plating is formed on the cured product of the photosensitive resin composition), and photosensitive resin composition for solder resist Product (printed wiring board using a cured product of a photosensitive resin composition as a solder resist), a photosensitive resin composition for a rewiring formation layer of a wafer level package (a cured product of a photosensitive resin composition used as a rewiring formation layer Wafer level package), photosensitive resin composition for rewiring formation layer of fan-out wafer level package (fan-out wafer level package with cured product of photosensitive resin composition as rewiring formation layer), fan-out panel level package Photosensitive resin composition for rewiring forming layer (fan-out panel level package with cured product of photosensitive resin composition as rewiring forming layer), photosensitive resin composition for buffer coating (cured product of photosensitive resin composition can be suitably used as a semiconductor device with a buffer coat) and a photosensitive resin composition for an insulating layer for a display (a display with a cured product of a photosensitive resin composition as an insulating layer).

[Photosensitive film]
The photosensitive resin composition of the present invention can be applied to photosensitive films. A photosensitive film may comprise a support and a photosensitive resin composition layer formed on the support. The photosensitive resin composition layer is a layer made of the photosensitive resin composition described above. Moreover, the photosensitive film may comprise a support, a photosensitive resin composition layer, and a protective film in this order.

Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film and the like, and polyethylene terephthalate film is particularly preferred.

Commercially available supports include, for example, Oji Paper Co., Ltd. product names "Alphan MA-410" and "E-200C", Tamapoly Co., Ltd. product names "GF-1" and "GF-8", Shin-Etsu Film Co., Ltd. and polyethylene terephthalate films such as the PS series such as the product name "PS-25" manufactured by Teijin Limited, but are not limited thereto. These supports preferably have a release agent such as a silicone or non-silicone coating applied to the surface to facilitate removal. Examples of the support whose surface is treated with such a release agent include "AL-5" manufactured by Lintec Corporation. The thickness of the support is preferably in the range of 5 μm to 100 μm, more preferably in the range of 10 μm to 50 μm.

The thickness of the photosensitive resin composition layer is not particularly limited, and can be, for example, 1 μm or more and 100 μm or less. Among them, it is preferably 2 μm or more, more preferably 4 μm or more, and preferably 50 μm or less, more preferably 30 μm or less.

The photosensitive resin composition layer may be protected with a protective film. By protecting the photosensitive resin composition layer with the protective film, it is possible to suppress adhesion of dust and scratches on the surface of the photosensitive resin composition layer. As the protective film, for example, a film made of the same material as the support can be used. Although the thickness of the protective film is not particularly limited, it is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, even more preferably in the range of 10 μm to 30 μm. The protective film preferably has a lower adhesive strength between the photosensitive resin composition layer and the protective film than the adhesive strength between the photosensitive resin composition layer and the support.

A photosensitive film can be produced, for example, by coating a photosensitive resin composition on a support and drying the component (G) if necessary.

[Semiconductor package substrate]
The semiconductor package substrate of the present invention includes an insulating layer formed from a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring layer, an interlayer insulating layer, a buffer coat film or a solder resist.

Specifically, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-described photosensitive resin composition, and a cured product of the photosensitive resin composition is used as the insulating layer. Specifically, the method for manufacturing a semiconductor package substrate includes:
(I) forming a photosensitive resin composition layer containing the photosensitive resin composition of the present invention on a circuit board;
(II) a step of irradiating the photosensitive resin composition layer with actinic rays, and (III) a step of developing the photosensitive resin composition layer,
in that order.

<Step (I)>
Examples of the method of forming the photosensitive resin composition layer include a method of directly applying a resin varnish containing the photosensitive resin composition onto a circuit board, and a method of using the photosensitive film.

When a resin varnish containing a photosensitive resin composition is directly applied onto a circuit board, the component (G) is dried and volatilized to form a photosensitive resin composition layer on the circuit board.

Examples of resin varnish coating methods include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, and roll coating. , knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spin coating method, slit coating method, spray coating method, dip coating method, hot melt coating method, bar coating method, applicator method, air knife coating method, A curtain flow coating method, an offset printing method, a brush coating method, a full-surface printing method using a screen printing method, and the like can be mentioned.

The resin varnish may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Also, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

After applying the resin varnish, it is dried in a hot air oven or a far-infrared oven, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. Thus, a photosensitive resin composition layer is formed on the circuit board.

Examples of circuit substrates include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. Here, the circuit board refers to a substrate having a patterned conductor layer (circuit) formed on one side or both sides of the support substrate as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

On the other hand, when a photosensitive film is used, the photosensitive resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the lamination step, when the photosensitive film has a protective film, after removing the protective film, the photosensitive film and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed and It is crimped to the circuit board while heating. In the case of the photosensitive film, a method of laminating it on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

Although the conditions for lamination are not particularly limited, for example, the crimping temperature (laminating temperature) is preferably 70° C. to 140° C., and the crimping pressure is preferably 1 kgf/cm ² to 11 kgf/cm ² (9.8 ×10 ⁴ N/m ² to 107.9×10 ⁴ N/m ² ), the pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. preferable. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to.

<Step (II)>
After the photosensitive resin composition layer is provided on the circuit board, an exposure step is performed in which a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays through a mask pattern. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The irradiation dose of ultraviolet rays is approximately 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a circuit board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact.

In step (II), vias can be formed using a via pattern such as a round hole pattern as the mask pattern. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less. Although the lower limit is not particularly limited, it can be 0.1 μm or more, 0.5 μm or more, or the like.

<Step (III)>
After the exposure step, a pattern can be formed by performing a development step of removing the unexposed portions of the photosensitive resin composition layer with a developer. Development is usually carried out by wet development.

In the case of wet development, safe and stable developing solutions with good operability such as alkaline solutions, aqueous developing solutions and organic solvents are used. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately employed.

Examples of the alkaline aqueous solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.

These alkaline aqueous solutions may contain surfactants, antifoaming agents and the like to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8-12, more preferably in the range of 9-11. Further, the base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. They are monobutyl ether, cyclopentanone, and cyclohexanone.

The concentration of such an organic solvent is preferably 2% by mass to 90% by mass with respect to the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, two or more developing methods may be used in combination. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Thermal curing (post-baking) process>
After completion of the step (III), a heat curing (post-baking) step is performed as necessary. It is possible that the curing of the photosensitive resin composition layer proceeds in the above steps (I) to (III), but the curing of the photosensitive resin composition is further advanced by the heat curing step, and the insulation with excellent mechanical strength is obtained. You can get layers. The post-baking process includes a heating process using a clean oven. The atmosphere during thermosetting may be in the air or in an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, preferably 150° C. to 250° C. for 20 minutes to 180 minutes, more preferably It is selected in the range of 160° C. to 230° C. for 30 minutes to 120 minutes.

<Other processes>
The method for manufacturing a semiconductor package substrate may further include a drilling step and a desmear step after forming an insulating layer as a cured photosensitive resin composition layer. These steps may be performed according to various methods known to those skilled in the art for use in the manufacture of semiconductor package substrates.

After forming the insulating layer, if desired, the insulating layer formed on the circuit board is subjected to a drilling process to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferred.

A desmear process is a process of desmearing. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Dry desmearing includes, for example, desmearing using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear processing apparatuses, suitable examples for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30° C. to 50° C. for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

Regardless of whether the insulating layer is formed as a rewiring forming layer, an interlayer insulating layer, or a solder resist, a drilling step and a desmear step may be performed after the thermosetting step. Moreover, in the method for manufacturing a semiconductor package substrate, a plating step may be further performed.

A plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by sputtering after forming the insulating layer, or may be formed by combining electroless plating and electrolytic plating, or forming a plating resist having a pattern opposite to that of the conductor layer, The conductor layer may be formed only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

A semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-described photosensitive resin composition, and a cured product of the photosensitive resin composition is used as a rewiring formation layer. Specifically, the method for manufacturing a semiconductor package substrate includes:
(A) a step of laminating a temporary fixing film on a substrate;
(B) temporarily fixing the semiconductor chip on the temporary fixing film;
(C) forming a sealing layer on the semiconductor chip;
(D) a step of peeling the substrate and the temporary fixing film from the semiconductor chip;
(E) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed;
(F) forming a rewiring layer as a conductor layer on the rewiring forming layer;
(G) forming a solder resist layer on the rewiring layer;
including. Further, the method for manufacturing the semiconductor chip package includes:
(H) a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to singulate them;
may contain

<Step (A)>
Step (A) is a step of laminating a temporary fixing film on a substrate. The conditions for laminating the substrate and the temporary fixing film are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding pressure is preferably 1 kgf/cm ² to 11 kgf. /cm ² , the pressure bonding time is preferably 5 seconds to 300 seconds, and the lamination is preferably performed under a reduced pressure of 20 mmHg or less. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to.

Examples of substrates include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel and cold-rolled steel plate (SPCC); FR-4 substrates and the like; A heat-cured substrate; a substrate made of bismaleimide triazine resin such as BT resin; and the like.

Any material that can be peeled off from the semiconductor chip and that can temporarily fix the semiconductor chip can be used for the temporary fixing film. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

<Step (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. Temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder, a die bonder, or the like. The layout and the number of semiconductor chips to be arranged can be appropriately set according to the shape and size of the temporary fixing film, the target production volume of the semiconductor package, and the like. For example, the semiconductor chips may be arranged in a matrix of multiple rows and multiple columns and temporarily fixed.

<Step (C)>
Step (C) is a step of forming a sealing layer on the semiconductor chip. Any insulating material can be used for the sealing layer, and the photosensitive resin composition described above may be used. The sealing layer is usually formed by a method including the steps of forming a sealing resin composition layer on the semiconductor chip and thermally curing the resin composition layer to form the sealing layer.

Formation of the sealing resin composition layer is preferably performed by a compression molding method. In the compression molding method, the semiconductor chip and the encapsulating resin composition are usually placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to seal the semiconductor chip. forming a resin composition layer for

A specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. In addition, the sealing resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the encapsulating resin composition is attached to the lower mold together with the substrate and the temporary fixing film. Thereafter, the upper mold and the lower mold are clamped, and heat and pressure are applied to the encapsulating resin composition for compression molding.

Further, the specific operation of the compression molding method may be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. A sealing resin composition is placed on the lower mold. Also, the semiconductor chip is attached to the upper mold together with the base material and the temporary fixing film. After that, the upper mold and the lower mold are clamped so that the sealing resin composition placed on the lower mold is in contact with the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

Molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted so as to achieve good encapsulation. For example, the temperature of the mold during molding is preferably a temperature at which the encapsulating resin composition can exhibit excellent compression moldability, preferably 80° C. or higher, more preferably 100° C. or higher, and particularly preferably 120° C. or higher. , preferably 200° C. or lower, more preferably 170° C. or lower, particularly preferably 150° C. or lower. The pressure applied during molding is preferably 1 MPa or higher, more preferably 3 MPa or higher, particularly preferably 5 MPa or higher, and preferably 50 MPa or lower, more preferably 30 MPa or lower, and particularly preferably 20 MPa or lower. The curing time is preferably 1 minute or longer, more preferably 2 minutes or longer, particularly preferably 5 minutes or longer, and preferably 60 minutes or shorter, more preferably 30 minutes or shorter, and particularly preferably 20 minutes or shorter. Usually, the mold is removed after forming the encapsulating resin composition layer. The mold may be removed before or after heat curing of the encapsulating resin composition layer.

The compression molding method may be performed by discharging the sealing resin composition filled in the cartridge into a lower mold.

<Step (D)>
Step (D) is a step of peeling off the substrate and the temporary fixing film from the semiconductor chip. As for the peeling method, it is desirable to employ an appropriate method according to the material of the temporary fixing film. Examples of the peeling method include a method of heating, foaming, or expanding the temporary fixing film to peel it. Moreover, as a peeling method, for example, a method of irradiating the temporary fixing film with ultraviolet rays through the base material to reduce the adhesive strength of the temporary fixing film and peel it off can be used.

In the method of peeling by heating, foaming or expanding the temporary fixing film, the heating conditions are usually 100° C. to 250° C. for 1 second to 90 seconds or 5 minutes to 15 minutes. In the method of removing the temporary fixing film by irradiating it with ultraviolet rays to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet rays is usually 10 mJ/cm ² to 1000 mJ/cm ² .

<Step (E)>
Step (E) is a step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the substrate and the temporary fixing film have been removed. The photosensitive resin composition of the present invention is used for the rewiring formation layer. The method for forming the rewiring forming layer is the same as the method for forming the photosensitive resin composition layer in step (I) in the first embodiment.

When forming the rewiring layer, a via hole may be formed in the rewiring layer for interlayer connection between the semiconductor chip and the rewiring layer.

Via holes are usually formed by exposing the surface of the photosensitive resin composition layer for forming the rewiring layer through a mask pattern and irradiating actinic rays through a mask pattern, and developing the non-exposed areas not irradiated with actinic rays. It can be formed by performing a developing step for removing. The irradiation dose and irradiation time of actinic rays can be appropriately set according to the photosensitive resin composition layer. The exposure method includes, for example, a contact exposure method in which the mask pattern is brought into close contact with the photosensitive resin composition layer for exposure, and a non-contact method in which the mask pattern is not brought into close contact with the photosensitive resin composition layer and is exposed using parallel rays. An exposure method and the like can be mentioned. The actinic ray, alkaline aqueous solution, and exposure/development method are as described above.

Although the shape of the via hole is not particularly limited, it is generally circular (substantially circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 20 μm or less, and preferably 0.1 μm or more, preferably 0.5 μm or more, and more preferably 1.0 μm or more. Here, the top diameter of the via hole means the diameter of the opening of the via hole on the surface of the rewiring layer.

<Step (F)>
Step (F) is a step of forming a rewiring layer as a conductor layer on the rewiring forming layer. The method of forming the rewiring layer on the rewiring forming layer can be the same as the method of forming the conductor layer on the insulating layer in the first embodiment. Alternatively, the steps (E) and (F) may be repeated to alternately build up the rewiring layers and the rewiring formation layers (build-up).

<Step (G)>
Step (G) is a step of forming a solder resist layer on the rewiring layer. Any insulating material can be used as the material of the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferable from the viewpoint of easiness in manufacturing semiconductor chip packages. Moreover, you may use the photosensitive resin composition of this invention.

Moreover, in the step (G), a bumping process for forming bumps may be performed as necessary. Bumping can be performed by a method such as solder balls or solder plating. Formation of via holes in the bumping process can be performed in the same manner as in step (E).

The method for manufacturing a semiconductor chip package may include step (H) in addition to steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages to separate them into pieces. The method of dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[Semiconductor device]
Examples of semiconductor devices on which the above-described semiconductor chip package is mounted include electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (e.g. , motorcycles, automobiles, trains, ships, aircraft, etc.).

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the description below, unless otherwise specified, "parts" and "%" mean "mass parts" and "mass%", respectively.

<Synthesis Example 1: Synthesis of Polyimide Precursor A-1>
51.8 g of 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) was placed in a 2 L separable flask, and 500 mL of N-methyl-2-pyrrolidone was added to the separator. It was placed in a blue flask and stirred at room temperature. Furthermore, 20.0 g of 4,4′-diaminophenyl oxide (ODA) was added to the separable flask, and at the same time, the internal temperature of the separable flask reached 40° C. with an oil bath, and polymerization was carried out for 20 hours.

Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added. Stirred. The obtained reaction solution was heated to 40° C., 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine and 20 g of triethylamine were added and stirred for 3 hours.

Next, the resulting reaction solution was added dropwise to 6 L of ultrapure water to precipitate polyimide precursor A-1 for purification. After the purified polyimide precursor A-1 was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 70 g of polyimide precursor A-1 having the following structure. The weight average molecular weight of polyimide precursor A-1 was measured by gel permeation chromatography (converted to standard polystyrene) and found to be 40,000.

<Synthesis Example 2: Synthesis of Polyimide Precursor A-2>
Put 29.4 g of 3,3′,4,4′-biphenyltetracarboxylic dianhydride (sBPDA) in a 2 L separable flask, put 500 mL of N-methyl-2-pyrrolidone in a separable flask, and heat at room temperature. Stirred. Furthermore, 41.0 g of 2,2′-bis(4-aminophenoxyphenyl)propane (BAPP) was added to the separable flask, and at the same time, the internal temperature of the separable flask was heated to 40° C. in an oil bath. Time polymerized.

Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, and 8.8 g of ethylene carbonate was added. Stirred. The obtained reaction solution was heated to 40° C., 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine and 20 g of triethylamine were added and stirred for 3 hours.

Next, the resulting reaction solution was added dropwise to 6 L of ultrapure water to precipitate polyimide precursor A-2 for purification. After the purified polyimide precursor A-2 was separated by filtration, it was vacuum-dried under heating at 80° C. to obtain 65 g of polymer A-2 having the following structure. The weight average molecular weight of polyimide precursor A-2 was measured by gel permeation chromatography (converted to standard polystyrene) and found to be 50,000.

<Preparation of photosensitive resin composition>
Each component was dissolved in 280 parts by mass of γ-butyrolactone (GBL) solvent according to the blending amounts (unit: parts by mass) shown in the table below to prepare each photosensitive resin composition. In the table, the content of component (A) and the content of component (D) represent the content when the non-volatile component of the photosensitive resin composition is 100% by mass.

・Ｃ－１：下記構造で表される化合物（Ｉｒｇａｃｕｒｅ－ＯＸＥ０２：ＢＡＳＦ社製）

・Ｄ－１：ニットレジンクマロン Ｈ－１００、日塗化学社製
・Ｄ－２：ニットレジンクマロン Ｖ－１２０Ｓ、日塗化学社製
・Ｄ－３：ニットレジンクマロン Ｖ－１２０、日塗化学社製
・Ｅ－１：下記構造式で表される化合物

Abbreviations, etc. in the table are as follows.
· A-1: Polyimide precursor A-1 synthesized in Synthesis Example 1
· A-2: Polyimide precursor A-2 synthesized in Synthesis Example 2
· B-1: a compound represented by the following structural formula

· C-1: a compound represented by the following structure (Irgacure-OXE02: manufactured by BASF)

・D-1: Knit resin cumarone H-100, manufactured by Nichinuri Chemical ・D-2: Knit resin cumarone V-120S, manufactured by Nichinuri Chemical ・D-3: Knit resin cumarone V-120, manufactured by Nihon Coating Chemical Co., Ltd. E-1: A compound represented by the following structural formula

<Evaluation of Limiting Resolution>
A 10 μm-thick layer of copper plating was laminated on a silicon wafer, and the substrate was roughened with a 1% hydrochloric acid aqueous solution for 10 seconds. After coating the photosensitive resin composition, it was heated on a hot plate at 120° C. for 5 minutes to form a photosensitive resin composition layer. This is called a laminate.

The produced laminate was exposed to ultraviolet light (wavelength: 365 nm, intensity: 40 mW/cm ² ). The optimum exposure amount was set in the range of 50 mJ/cm ² to 1000 mJ/cm ² . As an exposure pattern, a quartz glass mask was used for drawing circular holes (vias) with openings of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm.

Next, the entire surface of the photosensitive resin composition layer on the laminate is sprayed with cyclopentanone as a developer at a spray pressure of 0.2 MPa for an optimum time of 30 to 200 seconds, followed by development. , and 2-methoxy-1-methylethyl acetate (PGMEA) at a spray pressure of 0.2 MPa for 30 seconds. Further, heat treatment was performed at 200° C. for 120 minutes to cure the photosensitive resin composition layer.

The diameters of the bottoms of vias with openings of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed by SEM (1000× magnification) and measured. The minimum size that can be opened was taken as the resolution limit.

<Evaluation of dielectric properties (dielectric constant, dielectric loss tangent)>
The photosensitive resin composition blended according to the composition shown in the above table was coated on the release-treated PET film using a blade so as to have a thickness of 140 μm. After heating the solution on PET at 80° C. for 20 minutes using a heater, the photosensitive resin composition layer film was peeled off from the PET film, and the photosensitive resin composition layer film was attached to the metal frame using a heat-resistant tape. It was pasted and further cured at 250° C. for 2 hours to prepare a film for measuring physical properties.

A test piece having a width of 2 mm and a length of 80 mm was cut from the film for measuring physical properties. The dielectric loss tangent and dielectric constant of the cut test piece were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies. .

In Examples 1 to 6, it was possible to obtain cured products excellent in limited resolution and excellent dielectric properties. On the other hand, Comparative Example 1, which does not contain component (D), was not satisfactory in limited resolution. In addition, in Examples 1 to 6, even if the component (E) is not contained, although there is a difference in degree, it was confirmed that by increasing the exposure dose, the same results as in the above Examples were obtained. is doing.

Claims (8)

(A) a polyimide precursor,
(B) a cross-linking agent;
(C) a photoradical generator, and (D) at least one resin selected from the group consisting of indene resins and coumarone-indene resins,
A photosensitive resin composition containing 2. The photosensitive resin composition according to claim 1, further comprising (E) a sensitizer. 3. The photosensitive resin composition according to claim 1, wherein the content of component (D) is 1% by mass or more and 10% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. The photosensitive material according to any one of claims 1 to 3, wherein the content of component (A) is 70% by mass or more and 98% by mass or less when the non-volatile component of the photosensitive resin composition is 100% by mass. elastic resin composition. A photosensitive film comprising a support and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 4 formed on the support. A semiconductor package substrate comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 4. A semiconductor device comprising the semiconductor package substrate according to claim 6 . A step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of claims 1 to 4 on a circuit board;
A step of irradiating the photosensitive resin composition layer with an actinic ray;
and a step of developing the photosensitive resin composition layer.