Photosensitive resin composition

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

Technical Field

[0001] The present invention relates to a photosensitive resin composition. Further, the present invention relates to a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate, which are obtained using the photosensitive resin composition.

Background Art

[0002] Conventionally, polyimide resins having excellent heat resistance and insulation properties have been used for the insulating layers of semiconductor devices. Further, since polyimide resins have low solubility in solvents, in photosensitive resin compositions, they are used in the state of polyimide precursors, and after forming an insulating layer or the like, the polyimide precursor is cyclized to form an insulating layer (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0004] In recent years, with the increase in the speed and capacity of communication in communication devices, excellent dielectric properties such as excellent resolution and low dielectric constant and dielectric tangent of the cured product are required also for the photosensitive resin composition used for the semiconductor package substrate of communication devices.

[0005] The present invention has been made in view of the above problems, and an object of the present invention is to provide a photosensitive resin composition excellent in limit resolution and dielectric properties of the cured product, a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate, which are obtained using the photosensitive resin composition.

Means for Solving the Problems

[0006] As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by incorporating a polyimide precursor, a crosslinking agent, a photo radical generator, and at least one resin selected from the group consisting of indene resins and coumarone-indene resins into a photosensitive resin composition, and the present invention has been completed.

[0007] That is, the present invention includes the following. [1] A photosensitive resin composition containing (A) a polyimide precursor, (B) a crosslinking agent, (C) a photo radical generator, and (D) at least one resin selected from the group consisting of indene resins and coumarone-indene resins. [2] The photosensitive resin composition according to [1], further containing (E) a sensitizer. [3] The photosensitive resin composition 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 non-volatile components of the photosensitive resin composition are 100% by mass. [4] The photosensitive resin composition according to 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 components of the photosensitive resin composition are 100% by mass. [5] A photosensitive film in which a photosensitive resin composition layer composed of the photosensitive resin composition according to any one of [1] to [4] is formed on a support. [6] A semiconductor package substrate including an insulating layer formed of 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] A method for manufacturing a semiconductor package substrate, including a step of 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 actinic rays, and a step of developing the photosensitive resin composition layer.

Advantages of the Invention

[0008] According to the present invention, there can be provided a photosensitive resin composition excellent in ultimate resolution and dielectric properties of a cured product, a photosensitive film, a semiconductor package substrate, a semiconductor device, and a method for manufacturing a semiconductor package substrate obtained by using the photosensitive resin composition.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the photosensitive resin composition, photosensitive film, semiconductor package substrate, semiconductor device, and method for manufacturing a semiconductor package substrate of the present invention will be described in detail. In the following description, "dielectric constant" represents "relative dielectric constant" unless otherwise specified.

[0010] [Photosensitive Resin Composition] The photosensitive resin composition of the present invention contains (A) a polyimide precursor, (B) a crosslinking agent, (C) a photo radical generator, and (D) at least one resin selected from the group consisting of an indene resin and a coumarone-indene resin. By combining the components (A) to (D) and containing them in the photosensitive resin composition, a cured product excellent in ultimate resolution and dielectric properties can be obtained.

[0011] The photosensitive resin composition of the present invention is suitable as a negative photosensitive resin composition.

[0012] The photosensitive resin composition may further contain an arbitrary component in combination with the components (A) to (D). Examples of the arbitrary component include (E) a sensitizer, (F) other additives, and (G) a solvent. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

[0013] <(A) Polyimide Precursor> The photosensitive resin composition contains (A) a polyimide precursor as the component (A). By containing the component (A) in the photosensitive resin composition, a cured product excellent in ultimate resolution and dielectric properties can be obtained. The component (A) may be used alone or in combination of two or more.

[0014] (A) component can use a resin having a plurality of amino acid structures and / or amino acid ester structures. From the viewpoint of obtaining a cured product with excellent limit resolution and excellent dielectric properties, it is preferable that the (A) component has a structural unit represented by the following formula (A-1).

Chemical formula

[0015] 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 preferable. Examples of the tetravalent organic group having 6 to 40 carbon atoms include, for example, an aromatic group or an alicyclic aliphatic group in which the -COOR 1 group and the -COOR 2 group and the -CONH- group are in ortho positions to each other. Examples of such groups include the groups (i) to (ix). Also, a group formed by combining two or more of the groups (i) to (ix) may be used. Among them, as A, the following exemplified tetravalent organic groups are preferable, and the group (viii) and the group (ix) are more preferable. In the formula, * represents a bond.

Chemical formula

[0016] In formula (A-1), each B independently represents a divalent organic group. The divalent organic group preferably has an aromatic ring. Examples of the divalent organic group include the groups (1a) to (19a) exemplified below. Also, a group formed by combining two or more of the groups (1a) to (19a) may be used. As B, the group (2a) and the group (19a) are preferable. In the formula, * represents a bond.

Chemical formula

[0017] The divalent organic group may have a substituent. Examples of the substituent include linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group; halogen atoms such as fluorine atom, chlorine atom, bromine atom; alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group; hydroxy group; halogen atom-substituted alkyl groups such as trifluoromethyl group, etc., and an alkyl group is preferred. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as "secondary substituent"). The substituents may be included alone or in combination of two or more.

[0018] R in formula (A-1) 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include saturated aliphatic groups having 1 to 4 carbon atoms; reactive groups that can be polymerized by radicals generated by heat or light, i.e., radical-reactive groups, etc., and it is preferably a radical-reactive group. R in formula (A-1) 1 and R 2 are each independently preferably at least one is a radical-reactive group, and more preferably both are radical-reactive groups. As the radical-reactive group, a group represented by the following formula (A-2) is preferred. [Chemistry] (In the formula, R 4 ~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.)

[0019] R in formula (A-2) 4 ~R 6Each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, etc., and among them, a methyl group is preferred.

[0020] As the saturated aliphatic group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, an n-butyl group, etc.

[0021] In formula (A-2), p represents an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 2.

[0022] R in formula (A-1) 1 and R 2 are each independently preferably at least one of them is a radical-reactive group, more preferably at least one of them is a group represented by formula (A-2), and even more preferably both R 1 and R 2 are both groups represented by formula (A-2).

[0023] In formula (A-1), n represents an integer of 5 to 200, preferably an integer of 5 to 150, more preferably an integer of 5 to 100, and even more preferably an integer of 5 to 70.

[0024] Specific examples of component (A) can include the following compounds (A1) to (A2). However, component (A) is not limited to these specific examples. In the formula, n represents an integer of 5 to 200.

Chemical formula

[0025] The weight average molecular weight of component (A) is preferably 5000 or more, more preferably 10000 or more, still more preferably 50000 or more, and preferably 1000000 or less, more preferably 500000 or less, still more preferably 200000 or less, from the viewpoint of significantly obtaining the effects of the present invention. The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC) method.

[0026] There is no particular limitation on the production method of component (A). Component (A) can usually be obtained by reacting a tetracarboxylic dianhydride and a diamine compound. Component (A) can be produced, for example, by the production methods described in JP-A-2015-209461, JP-A-2015-214680, JP-A-2017-219850, or JP-A-2018-146964.

[0027] The content of component (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still 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, and preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, when the non-volatile components of the photosensitive resin composition are 100% by mass, from the viewpoint of significantly obtaining the effects of the present invention. In the present invention, the content of each component in the photosensitive resin composition is a value when the non-volatile components in the photosensitive resin composition are 100% by mass, unless otherwise specified.

[0028] <(B) Crosslinking agent> The photosensitive resin composition contains a (B) crosslinking agent as component (B). However, those corresponding to component (A) are excluded from component (B). When the photosensitive resin composition is irradiated with actinic rays and radicals are generated from a photo radical generator, a crosslinking reaction of component (B) etc. occurs and it becomes insoluble in the developer. Therefore, during development, it becomes possible to selectively remove the photosensitive resin composition except for the portions where the crosslinking reaction has progressed, and a negative-type pattern can be advantageously formed. Component (B) may be used alone or in combination of two or more.

[0029] (B) As a component, a compound capable of promoting a crosslinking reaction during development can be used. Such a compound is preferably a compound having an ethylenically unsaturated bond, and more preferably a compound having an ethylenically unsaturated bond and at least one of the carbon atoms at the α-position of the ethylenically unsaturated bond being bonded to a carbonyl group or an aromatic group. The carbon atom at the α-position of the ethylenically unsaturated bond refers to the first carbon atom adjacent to the carbon atom bonded by a carbon-carbon double bond.

[0030] The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, the (B) component may contain a group having an ethylenically unsaturated bond (hereinafter, may be appropriately referred to as an "ethylenically unsaturated group"). The ethylenically unsaturated group is usually a monovalent group, and examples thereof include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. From the viewpoint of the reactivity of photoradical polymerization, a (meth)acryloyl group and a phenylethynyl group are preferred, and a (meth)acryloyl group is particularly preferred. The "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. Since the (B) component contains an ethylenically unsaturated bond, photoradical polymerization is possible. However, for performing photoradical polymerization under general conditions, a compound having a carbonyl group or an aromatic group at at least one of the α-positions of the ethylenically unsaturated bond is preferred. The number of ethylenically unsaturated bonds per molecule of the (B) component is preferably one or more, more preferably two or more. Also, when the (B) component contains two or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be the same or different.

[0031] (B) As a component, a compound represented by the following general formula (B-1) is preferred.

Chemical formula

[0032] R 1b each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, an s-butyl group, a t-butyl group, etc. Among them, R 1b is preferably a hydrogen atom or a methyl group.

[0033] Z 1b each independently represents 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 a linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom. As the linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkylene group having 1 to 10 carbon atoms is preferable, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferable. 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, etc., and a methylene group is preferable. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such a group include those shown below. In the formula, "*" represents a bond, and a represents an integer of 1 to 23.

Chemical formula

[0034] The arylene group which may contain an oxygen atom is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 15 carbon atoms, and even more preferably an arylene group having 6 to 10 carbon atoms. Examples of such arylene groups include a phenylene group and a naphthylene group. Further, 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 to 23. [Chemical formula]

[0035] 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 more preferably a linear or branched alkenylene group having 2 to 6 carbon atoms. Examples of such alkenylene groups include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group. Further, the alkenylene group may be an oxyalkenylene group containing 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 to 23. The propenylene group is preferred as the alkenylene group. [Chemical formula]

[0036] Among them, Z 1b is preferably a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom, and more preferably a methylene group.

[0037] A 1brepresents a linear, cyclic or branched nb-valent organic group having 1 to 10 carbon atoms. Examples of the nb-valent organic group include an nb-valent hydrocarbon group which may contain an oxygen atom, an nb-valent group derived from bisphenol, an nb-valent group derived from fluorene, an nb-valent group 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 an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom and an nb-valent aromatic hydrocarbon group which may contain an oxygen atom, and an nb-valent aliphatic hydrocarbon group which may contain an oxygen atom is preferred. A 1b Specific examples of the group represented by are, for example, those shown below. In the formula, " * " represents a bond.

Chemical formula

[0038] nb represents a positive integer of 2 to 6, preferably represents a positive integer of 2 to 5, more preferably represents an integer of 2 to 4, and represents 2 or 3.

[0039] As the component (B), a compound represented by the following general formula (B-2) is preferred.

Chemical formula

[0040] R 2b represents a hydrogen atom or a methyl group, and a methyl group is preferred.

[0041] Specific examples of the component (B) include the following compounds (CL-1) to (CL-11). However, the component (B) is not limited thereto.

Chemical formula

Chemical formula

[0042] (Component (B) can be a commercially available product. Examples of commercially available products include NK Ester-D-TMP, 4G, 9G, 14G, 23G, DCP, etc. manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0043] Regarding the content of component (B), from the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components of the photosensitive resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, 2% by mass or more, 3% by mass or more, and preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less.)

[0044] <(C) Photo radical generator> The photosensitive resin composition contains (C) a photo radical generator. Component (C) generates radicals upon irradiation with actinic rays, and the crosslinking reaction can proceed by these radicals. In the photosensitive resin composition, the portion where the crosslinking reaction by radicals occurs hardens to form a cured product, and the resistance to the developer is improved. Therefore, during development, it is possible to selectively remove the photosensitive resin composition except for the portion where the crosslinking reaction has proceeded, and a negative-type pattern can be advantageously formed. Component (C) may be used alone or in combination of two or more. Also, components corresponding to components (A) to (B) are excluded from component (C).

[0045] Examples of component (C) include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone; acetophenone derivatives such as 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone; thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone; benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin, benzoin methyl ether; oximes such as 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; N-aryl glycines such as N-phenylglycine; peroxides such as benzoyl perchloride; aromatic biimidazoles; titanocenes; α-(n-octanesulfonyloxyimino)-4-methoxybenzyl cyanide; etc. Among them, from the viewpoint of photosensitivity, oximes are preferred as component (C).

[0046] As component (C), commercially available products can be used. Examples of commercially available products include "Irgacure - OX02", "Irgacure - OX04", etc. manufactured by BASF Corporation.

[0047] From the viewpoint of significantly obtaining the effects of the present invention, the content of component (C) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 17 parts by mass or less, still more preferably 15 parts by mass or less, based on 100 parts by mass of component (A).

[0048] As for the content of the component (C), from the viewpoint of remarkably obtaining the effects of the present invention, when the non-volatile components of the photosensitive resin composition are 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less.

[0049] <At least one resin selected from the group consisting of (D) indene resin and coumarone-indene resin> The photosensitive resin composition contains, as the component (D), at least one resin selected from the group consisting of (D) indene resin and coumarone-indene resin. By including the component (D) in the photosensitive resin composition, a cured product excellent in ultimate resolution and dielectric properties can be obtained. The component (D) may be used alone or in combination of two or more. Further, those corresponding to the above-described components (A) to (C) are excluded from the component (D).

[0050] The indene resin represents a polymer of monomers containing indene or alkyl indene as an essential monomer. The indene resin may be a copolymer of essential monomers such as indene and alkyl indene and optional monomers such as styrene derivatives such as styrene and alkyl styrene, and phenol derivatives such as di-t-butylhydroxybenzene. The coumarone-indene resin represents a polymer of monomers containing indene or alkyl indene and coumarone as essential monomers. The chroman-indene resin may be a copolymer of essential monomers such as indene or alkyl indene and coumarone and optional monomers such as styrene derivatives such as styrene and alkyl styrene, and phenol derivatives such as di-t-butylhydroxybenzene. The component (D) is at least one selected from the group consisting of indene resins and coumarone-indene resins, and is preferably a coumarone-indene resin. The coumarone-indene resin is preferably a copolymer of indene and coumarone, or a copolymer of indene, coumarone and a styrene derivative, and more preferably a copolymer of indene, coumarone and a styrene derivative.

[0051] The content ratio of the coumarone component in the coumarone-indene resin is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more. The upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less. The chroman component represents a repeating unit formed by polymerization of chroman.

[0052] 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 even more preferably 40 mol% or more. The upper limit is preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less. The indene component represents a repeating unit formed by polymerization of indene or alkyl indene.

[0053] When the coumarone-indene resin is a copolymer of indene, coumarone and a styrene derivative, the content ratio of the styrene derivative component is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. The upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less. The styrene derivative component represents a repeating unit formed by polymerization of styrene or a styrene derivative.

[0054] The softening point of the component (D) is preferably 90°C or higher, more preferably 100 - 180°C, and particularly preferably 120 - 180°C. The softening point of the component (D) refers to the value measured by the method described in JIS K2207.

[0055] (D) component can also use commercially available products. Examples of commercially available products of (D) component include "Knit Resin Cumarone H-100", "Knit Resin Cumarone V-120S", "Knit Resin Cumarone V-120" manufactured by Nitto Kasei Co., Ltd.

[0056] When the non-volatile components of the photosensitive resin composition are 100% by mass, the content of the (D) component is preferably 1% by mass or more, more preferably 1.3% by mass or more, still more preferably 1.5% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, from the viewpoint of significantly obtaining the effects of the present invention.

[0057] When the content of the (A) component when the non-volatile components of the photosensitive resin composition are 100% by mass is a1, and the content of the (D) component when the non-volatile components of the photosensitive resin composition are 100% by mass is d1, a1 / d1 is preferably 1 or more, more preferably 5 or more, still more preferably 8 or more, and preferably 200 or less, more preferably 150 or less, still more preferably 100 or less, from the viewpoint of significantly obtaining the effects of the present invention.

[0058] <(E) Sensitizer> The photosensitive resin composition may contain an (E) sensitizer as an optional component. By containing the (E) sensitizer in the photosensitive resin composition, it becomes possible to improve the photosensitivity of the photosensitive resin composition. The (E) component may be used alone or in combination of two or more. Also, those corresponding to the above-described (A) to (D) components are excluded from the (E) component.

[0059] 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; cyclic alkanes such as 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone; thiazoles such as 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone; coumarins such as 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; amines such as N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate; heterocyclic compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, 1-p-hydroxyphenyl-5-mercaptotetrazole; styrenes such as 2-(p-dimethylaminobenzoyl)styrene and the like.

[0060] Among them, as the component (E), from the viewpoint of remarkably obtaining the effects of the present invention, a heterocyclic compound is preferable, and a compound represented by the following general formula (E-1) is more preferable.

Chemical formula

[0061] 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 the linear or branched alkyl group having 1 to 7 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and the like. Among them, R 1e preferably represents a hydroxy group, a methoxy group, or a t-butoxy group having an oxygen atom, more preferably a hydrogen atom or a hydroxy group, and even more preferably a hydrogen atom.

[0062] R 1e The bonding position of R may be any of the ortho position, meta position, and para position with respect to the site of the phenylene group bonded to the nitrogen atom of mercaptotetrazole. However, from the viewpoint of remarkably obtaining the effects of the present invention, the para position is preferable.

[0063] The compound represented by (E-1) is preferably either the compound represented by the following (E-2) or the compound represented by the following (E-3).

Chemical formula

[0064] (E) The content of the component is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 17 parts by mass or less, still more preferably 15 parts by mass or less, based on 100 parts by mass of the component (A) from the viewpoint of significantly obtaining the effects of the present invention.

[0065] (E) The content of the component is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 17% by mass or less, still more preferably 15% by mass or less, when the non-volatile components of the photosensitive resin composition are 100% by mass from the viewpoint of significantly obtaining the effects of the present invention.

[0066] <(F) Other Additives> The photosensitive resin composition may further contain (F) other additives to the extent that it does not inhibit the object of the present invention. Examples of (F) other additives include adhesion aids; surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based 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 such as hydroquinone, phenothiazine, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as benton and montmorillonite; defoamers such as silicone-based, fluorine-based, and vinyl resin-based defoamers; flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters; and various additives such as heat-curable resins such as phenolic curing agents and cyanate ester-based curing agents can be added.

[0067] <(G) Solvent> The photosensitive resin composition may contain, as an optional component, (G) a solvent in combination with the non-volatile components such as the above-described components (A) to (F). The (G) solvent is a volatile component, and it is preferably one that can uniformly dissolve at least any one of the components (A) to (D) and the 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; ketone compounds having 2 to 6 carbon atoms such as acetone and 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; ester compounds having 3 to 9 carbon atoms such as methyl acetate, ethyl acetate, γ-butyrolactone, and methyl benzoate; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride, and 1,2-dichloroethane; nitrogen-containing compounds having 2 to 10 carbon atoms such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide.

[0068] In addition, examples of the component (G) include N-ethyl-2-pyrrolidone, tetrahydrofuran, N,N-dimethylacetamide, dimethyl sulfoxide, 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 butyl lactate. The component (G) may be used alone or in combination of two or more.

[0069] When the total amount of the photosensitive resin composition including the component (G) is 100% by mass, the content of the component (G) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 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. In addition, when the total amount of the photosensitive resin composition including the component (G) is 100% by mass, the content of the component (G) in the photosensitive resin composition layer of the photosensitive film is preferably 1% by mass or more, 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.

[0070] The photosensitive resin composition can be produced by mixing the above components (A) to (D) as essential components, appropriately mixing the above components (E) to (G) as optional components, and kneading or stirring as necessary by kneading means such as a three-roll mill, ball mill, bead mill, sand mill, or stirring means such as a super mixer or planetary mixer.

[0071] <Physical properties and uses of the photosensitive resin composition> The photosensitive resin composition exhibits the characteristic of excellent ultimate resolution. For example, exposure and development are performed using a mask for drawing round holes with an opening diameter of the exposure pattern of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm. In this case, the ultimate resolution, which is the minimum size that can be opened, is preferably 25 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less. The evaluation of the ultimate resolution can be measured according to the method described in the examples below.

[0072] The cured product obtained by thermally curing the photosensitive resin composition at 250 °C for 2 hours exhibits the characteristic of low dielectric constant (Dk). The dielectric constant at 23 °C is preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. The lower limit is not particularly limited, and it can be 1 or more, etc. The dielectric constant can be measured according to the method described in the examples below.

[0073] The cured product obtained by thermally curing the photosensitive resin composition at 250 °C for 2 hours exhibits the characteristic of low dielectric tangent (Df). The dielectric tangent at 23 °C is preferably 0.015 or less, more preferably 0.012 or less, and still more preferably 0.09 or less. The lower limit is not particularly limited, and it can be 0.0001 or more, etc. The dielectric tangent can be measured according to the method described in the examples below.

[0074] The use of the photosensitive resin composition of the present invention is not particularly limited, but it can be used in a wide range of applications where a photosensitive resin composition is used, such as photosensitive films, insulating resin sheets such as prepregs, silicon wafers, circuit boards (for laminated boards, multilayer printed wiring boards, etc.), solder resists, buffer coat films, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, component embedding resins, etc. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of the photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board having a cured product of the photosensitive resin composition as an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board having plating formed on a cured product of the photosensitive resin composition), and a photosensitive resin composition for solder resist (a printed wiring board having a cured product of the photosensitive resin composition as a solder resist), a photosensitive resin composition for a redistribution formation layer of a wafer-level package (a wafer-level package having a cured product of the photosensitive resin composition as a redistribution formation layer), a photosensitive resin composition for a redistribution formation layer of a fan-out wafer-level package (a fan-out wafer-level package having a cured product of the photosensitive resin composition as a redistribution formation layer), a photosensitive resin composition for a redistribution formation layer of a fan-out panel-level package (a fan-out panel-level package having a cured product of the photosensitive resin composition as a redistribution formation layer), a photosensitive resin composition for buffer coat (a semiconductor device having a cured product of the photosensitive resin composition as a buffer coat), and a photosensitive resin composition for an insulating layer for a display (a display having a cured product of the photosensitive resin composition as an insulating layer) can be preferably used.

[0075] [Photosensitive Film] The photosensitive resin composition of the present invention can be applied to a photosensitive film. The photosensitive film can include a support and a photosensitive resin composition layer formed on the support. The photosensitive resin composition layer is a layer composed of the above-described photosensitive resin composition. Further, the photosensitive film may include a support, a photosensitive resin composition layer, and a protective film in this order.

[0076] Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, triacetyl acetate film, etc., and polyethylene terephthalate film is particularly preferred.

[0077] Examples of commercially available supports include polypropylene films such as the product names "Alpha MA-410", "E-200C" manufactured by Oji Paper Co., Ltd., "GF-1", "GF-8" manufactured by Tamapoly Co., Ltd., and those manufactured by Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as the product name "PS-25" of the PS series manufactured by Teijin Limited, etc., but are not limited thereto. In order to facilitate removal of these supports, it is preferable that a release agent such as a silicone coating agent or a non-silicone coating agent is applied to the surface. 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, and more preferably in the range of 10 μm to 50 μm.

[0078] 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, preferably 50 μm or less, and more preferably 30 μm or less.

[0079] The photosensitive resin composition layer may be protected by a protective film. By protecting the photosensitive resin composition layer with a protective film, adhesion of dust and scratches to the surface of the photosensitive resin composition layer can be suppressed. As the protective film, for example, a film made of the same material as the above support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and even more preferably in the range of 10 μm to 30 μm. It is preferable that the adhesive force between the photosensitive resin composition layer and the protective film is smaller than the adhesive force between the photosensitive resin composition layer and the support.

[0080] The photosensitive film can be produced, for example, by applying a photosensitive resin composition onto a support and drying the component (G) as necessary.

[0081] [Semiconductor package substrate] The semiconductor package substrate of the present invention includes an insulating layer formed of a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a rewiring formation layer, an interlayer insulating layer, a buffer coat film, or a solder resist.

[0082] Specifically, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-described photosensitive resin composition, and the cured product of the photosensitive resin composition is used as an insulating layer. Specifically, the method for manufacturing a semiconductor package substrate includes: (I) A step of 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 this order.

[0083] <Step (I)> Examples of the method for 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 using the photosensitive film.

[0084] When directly applying a resin varnish containing the photosensitive resin composition onto a circuit board, a photosensitive resin composition layer is formed on the circuit board by drying and volatilizing the component (G).

[0085] Examples of the application method of the resin varnish include, for example, gravure coating method, micro gravure coating method, reverse coating method, kiss reverse coating method, die coating method, slot die method, lip coating method, comma coating method, blade coating method, roll coating method, 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, curtain flow coating method, offset printing method, brush painting method, full-surface printing method by screen printing method, etc.

[0086] The resin varnish may be applied in several portions, may be applied once, or may be applied by combining a plurality of different methods. Among them, the die coating method, which is excellent in uniform coating properties, is preferable. Also, in order to avoid foreign matter mixing, etc., it is preferable to carry out the coating process in an environment with less generation of foreign matter such as a clean room.

[0087] After applying the resin varnish, drying is carried out using a hot air furnace or an infrared furnace, etc. as necessary. The drying conditions are preferably 80°C to 120°C for 3 minutes to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0088] Examples of the circuit board include, for example, glass epoxy board, metal board, polyester board, polyimide board, BT resin board, thermosetting polyphenylene ether board, etc. Here, the circuit board refers to a board in which a conductor layer (circuit) subjected to pattern processing is formed on one or both sides of the support board as described above. Also, in a multilayer printed wiring board formed by alternately laminating a conductor layer and an insulating layer, a board in which one or both sides of the outermost layer of the multilayer printed wiring board are conductor layers (circuits) subjected to pattern processing is also included in the circuit board referred to here. Note that the surface of the conductor layer may be previously roughened by blackening treatment, copper etching, etc.

[0089] On the other hand, when using a photosensitive film, the photosensitive resin composition layer side is laminated on one or both sides of the circuit board using a vacuum laminator. In the lamination process, when the photosensitive film has a protective film, the protective film is removed, and then, if necessary, the photosensitive film and the circuit board are preheated, and the photosensitive resin composition layer is pressure-bonded to the circuit board while applying pressure and heat. In the case of the photosensitive film, a method of laminating it on the circuit board under reduced pressure by the vacuum lamination method is preferably used.

[0090] The lamination conditions are not particularly limited. For example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, the pressure-bonding pressure is preferably 1 kgf / cm 2 ~11 kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ), the pressure-bonding time is preferably 5 seconds to 300 seconds, and it is preferably laminated under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. Also, the lamination process may be a batch type or a continuous type using a roll. The vacuum lamination method can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Vacuum Applicator manufactured by Nippon Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll Type Dry Coater manufactured by Hitachi Industries Co., Ltd., the Vacuum Laminator manufactured by Hitachi AIC Inc., etc.

[0091] <Step (II)> After the photosensitive resin composition layer is provided on the circuit board, then, through a mask pattern, an exposure process of irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays is performed. Examples of the actinic rays include ultraviolet rays, visible light rays, electron beams, X-rays, etc., and ultraviolet rays are particularly preferred. The irradiation amount of ultraviolet rays is generally 10 mJ / cm 2 ~1000 mJ / cm 2It is so. As for the exposure method, there are 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 parallel light rays are used for exposure without bringing them into close contact, and either method may be used.

[0092] In step (II), as the mask pattern, for example, a via pattern such as a round hole pattern can be used to form vias. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, still more preferably 30 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more, 0.5 μm or more, etc.

[0093] <Step (III)> After the exposure step, a pattern can be formed by performing a development step of removing the unexposed portion of the photosensitive resin composition layer with a developer. Development is usually performed by wet development.

[0094] In the case of the above wet development, as the developer, a developer that is safe, stable, and has good operability, such as an alkaline solution, an aqueous developer, or an organic solvent, is used. As the development method, known methods such as spraying, rocking immersion, brushing, and scraping are appropriately employed.

[0095] Examples of the alkaline aqueous solution used as the developer include aqueous solutions of alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate, alkali metal phosphates such as sodium phosphate and potassium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred in that it contains no metal ions and does not affect the semiconductor chip.

[0096] These alkaline aqueous solutions may contain surfactants, defoamers, etc. to improve the development effect. The pH of the above alkaline aqueous solution is preferably in the range of 8 to 12, more preferably in the range of 9 to 11. Further, the base concentration of the above alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the above 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.

[0097] Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group with 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclopentanone, and cyclohexanone.

[0098] The concentration of such organic solvents is preferably 2% by mass to 90% by mass based on the total amount of the developer. Further, the temperature of such organic solvents can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0099] In pattern formation, two or more developing methods may be used in combination as necessary. Examples of the developing method include dip method, paddle method, spray method, high-pressure spray method, brushing, slapping, etc. The high-pressure spray method is suitable for improving the resolution. When the spray method is adopted, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0100] <Thermosetting (post-baking) process> After the completion of the above step (III), a thermal curing (post-baking) step is performed as necessary. In the above steps (I) to (III), the curing of the photosensitive resin composition layer may progress, but the thermal curing step can further progress the curing of the photosensitive resin composition to obtain an insulating layer with excellent mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The atmosphere during thermal curing may be air or 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, but are preferably in the range of 150°C to 250°C for 20 minutes to 180 minutes, more preferably in the range of 160°C to 230°C for 30 minutes to 120 minutes.

[0101] <Other steps> The method for manufacturing a semiconductor package substrate may further include a drilling step and a desmear step after forming an insulating layer as the cured photosensitive resin composition layer. These steps may be carried out according to various methods known to those skilled in the art used for manufacturing a semiconductor package substrate.

[0102] After forming the insulating layer, if desired, a drilling step is performed on the insulating layer formed on the circuit board to form via holes and through holes. The drilling step can be carried out by known methods such as drill, laser, plasma, etc., and if necessary, these methods can be combined. However, a laser drilling step using a carbon dioxide laser, a YAG laser, etc. is preferred.

[0103] The desmear step is a step of performing a desmear treatment. Generally, resin residues (smear) adhere to the inside of the openings formed in the drilling step. Since such smear may cause poor electrical connection, a treatment (desmear treatment) for removing the smear is carried out in this step.

[0104] The desmear treatment may be carried out by dry desmear treatment, wet desmear treatment, or a combination thereof.

[0105] Examples of dry desmear treatment include, for example, desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmear treatment apparatuses, suitable examples for the production of semiconductor package substrates include the microwave plasma apparatus manufactured by Nissin Corporation and the atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0106] Examples of wet desmear treatment include, for example, desmear treatment using an oxidizing agent solution. When performing desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling solution include "Swelling Dip Security Gun P" and "Swelling Dip Security Gun SBU" manufactured by Atotech Japan Co., Ltd. The swelling treatment is preferably carried out by immersing the substrate with formed vias or the like in a swelling solution heated to 60°C to 80°C for 5 minutes to 10 minutes. As the oxidizing agent solution, an alkaline permanganic acid aqueous solution is preferable, and examples thereof include a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably carried out by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. Commercially available products of the alkaline permanganic acid aqueous solution include, for example, "Concentrate Compact CP" and "Dosing Solution Security Gun P" manufactured by Atotech Japan Co., Ltd. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in a neutralizing solution at 30°C to 50°C for 3 minutes to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Security Ant P" manufactured by Atotech Japan Co., Ltd.

[0107] When carrying out a combination of dry desmear treatment and wet desmear treatment, the dry desmear treatment may be carried out first, or the wet desmear treatment may be carried out first.

[0108] Regardless of whether the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, after the thermosetting process, a drilling process and a desmear process may be performed. Further, in the method for manufacturing a semiconductor package substrate, a plating process may be further performed.

[0109] The plating process is a process of forming a conductor layer on the insulating layer. The conductor layer may be formed by sputtering after forming the insulating layer, may be formed by combining electroless plating and electroplating, or may form a plating resist having a pattern opposite to that of the conductor layer and form the conductor layer only by electroless plating. As a method for subsequent pattern formation, for example, a subtractive method, a semi-additive method, etc. known to those skilled in the art can be used.

[0110] The semiconductor package substrate according to the second embodiment of the present invention can be manufactured using the above-described photosensitive resin composition, and the cured product of the photosensitive resin composition is used as a rewiring formation layer. Specifically, the method for manufacturing a semiconductor package substrate is (A) A step of laminating a temporary fixing film on a base material, (B) A step of temporarily fixing a semiconductor chip on the temporary fixing film, (C) A step of forming a sealing layer on the semiconductor chip, (D) A step of peeling the base material and the temporary fixing film from the semiconductor chip, (E) A step of forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled, (F) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer, and (G) A step of forming a solder resist layer on the rewiring layer, is included. Further, the method for manufacturing the semiconductor chip package (H) A step of dicing and singulating a plurality of semiconductor chip packages into individual semiconductor chip packages, may be included.

[0111] <Step (A)> Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporary fixing film are not particularly limited. For example, the crimping temperature (lamination temperature) is preferably 70°C to 140°C, the crimping pressure is preferably 1 kgf / cm 2 ~11 kgf / cm 2 , the crimping time is preferably 5 seconds to 300 seconds, and it is preferably laminated under reduced pressure with an air pressure of 20 mmHg or less. Also, the lamination process may be a batch type or a continuous type using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include the Vacuum Applicator manufactured by Nichco Materials Co., Ltd., the Vacuum Pressure Laminator manufactured by Meiki Seisakusho Co., Ltd., the Roll Dry Coater manufactured by Hitachi Industries Co., Ltd., the Vacuum Laminator manufactured by Hitachi AIC Inc., and the like.

[0112] Examples of the base material include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, cold-rolled steel sheets (SPCC); substrates impregnated with epoxy resin or the like in glass fibers and subjected to thermosetting treatment, such as FR-4 substrates; substrates made of bismaleimide triazine resins such as BT resins; and the like.

[0113] The temporary fixing film can be peeled off from the semiconductor chip and any material that can temporarily fix the semiconductor chip can be used. Examples of commercially available products include "Revival Alpha" manufactured by Nitto Denko Corporation.

[0114] <Step (B)> Step (B) is a step of temporarily fixing a semiconductor chip on the temporary fixing film. The temporary fixing of the semiconductor chip can be performed using a device such as a flip chip bonder or a die bonder. The layout and the number of arrangements of the semiconductor chips can be appropriately set according to the shape and size of the temporary fixing film, the number of semiconductor packages to be produced, and the like. For example, the semiconductor chips may be aligned and temporarily fixed in a matrix shape with multiple rows and multiple columns.

[0115] <Step (C)> Step (C) is a step of forming a sealing layer on a semiconductor chip. Any insulating material can be used for the sealing layer, and the photosensitive resin composition described above may also be used. The sealing layer is usually formed by a method including a step of forming a resin composition layer for sealing on the semiconductor chip and a step of thermally curing this resin composition layer to form the sealing layer.

[0116] The formation of the resin composition layer for sealing is preferably performed by a compression molding method. In the compression molding method, usually, the semiconductor chip and the resin composition for sealing are placed in a mold, and pressure and, if necessary, heat are applied to the resin composition for sealing in the mold to form a resin composition layer for sealing covering the semiconductor chip.

[0117] The specific operation of the compression molding method can be, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. Also, a resin composition for sealing is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip coated with the resin composition for sealing is attached to the lower mold together with the base material and the temporary fixing film. Then, the upper mold and the lower mold are clamped, and heat and pressure are applied to the resin composition for sealing to perform compression molding.

[0118] Also, the specific operation of the compression molding method may be, for example, as follows. As a mold for compression molding, an upper mold and a lower mold are prepared. The resin composition for sealing 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. Then, the upper mold and the lower mold are clamped so that the resin composition for sealing placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0119] The molding conditions vary depending on the composition of the resin composition for sealing, and appropriate conditions can be adopted to achieve good sealing. For example, the temperature of the mold during molding is preferably a temperature at which the resin composition for sealing can exhibit excellent compression moldability, preferably 80 °C or higher, more preferably 100 °C or higher, particularly preferably 120 °C or higher, and preferably 200 °C or lower, more preferably 170 °C or lower, particularly preferably 150 °C or lower. Also, 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, particularly preferably 20 MPa or lower. The cure 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, particularly preferably 20 minutes or shorter. Usually, after the formation of the resin composition layer for sealing, the mold is removed. The removal of the mold may be performed before the thermosetting of the resin composition layer for sealing or after the thermosetting.

[0120] The compression molding method may be performed by discharging the resin composition for sealing filled in the cartridge onto the lower mold.

[0121] <Step (D)> Step (D) is a step of peeling the substrate and the temporary fixing film from the semiconductor chip. It is desirable to adopt an appropriate method according to the material of the temporary fixing film for the peeling method. Examples of the peeling method include a method of peeling by heating, foaming, or expanding the temporary fixing film. Also, examples of the peeling method include a method of irradiating ultraviolet rays through the substrate onto the temporary fixing film to reduce the adhesive force of the temporary fixing film and then peeling it.

[0122] 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. Also, in the method of irradiating ultraviolet rays to reduce the adhesive force of the temporary fixing film and then peeling it, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 ~1000 mJ / cm 2 is.

[0123] <Engineering (E)> Engineering (E) is a process of forming a redistribution layer as an insulating layer on the surface from which the base material of the semiconductor chip and the temporary fixing film have been peeled off. The redistribution layer uses the photosensitive resin composition of the present invention. The method of forming the redistribution layer is the same as the method of forming the photosensitive resin composition layer in process (I) of the first embodiment.

[0124] When forming the redistribution layer, via holes may be formed in the redistribution layer in order to make an interlayer connection between the semiconductor chip and the redistribution layer.

[0125] Via holes can usually be formed by performing an exposure process of irradiating actinic rays through a mask pattern on the surface of the photosensitive resin composition layer for forming the redistribution layer, and a development process of developing and removing the non-exposed portions not irradiated with actinic rays. The irradiation amount and irradiation time of the actinic rays can be appropriately set according to the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method of bringing the mask pattern into close contact with the photosensitive resin composition layer for exposure, and a non-contact exposure method of using parallel light rays for exposure without bringing the mask pattern into close contact with the photosensitive resin composition layer. The actinic rays, the alkaline aqueous solution, and the exposure and development method are as described above.

[0126] The shape of the via hole is not particularly limited, but 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, more preferably 1.0 μm or more. Here, the top diameter of the via hole refers to the diameter of the opening of the via hole on the surface of the redistribution layer.

[0127] <Process (F)> Step (F) is a step of forming a rewiring layer as a conductor layer on a rewiring formation layer. The method of forming a rewiring layer on a rewiring formation layer can be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Also, steps (E) and (F) may be repeated to alternately stack (build up) the rewiring layers and the rewiring formation layers.

[0128] <Step (G)> Step (G) is a step of forming a solder resist layer on the rewiring layer. As the material of the solder resist layer, any insulating material can be used. Among them, a photosensitive resin and a thermosetting resin are preferable from the viewpoint of ease of manufacturing a semiconductor chip package. Also, the photosensitive resin composition of the present invention may be used.

[0129] Also, in step (G), if necessary, bumping processing for forming bumps may be performed. The bumping processing can be performed by methods such as solder balls and solder plating. Also, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0130] 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 and separating them. The method of dicing a semiconductor chip package into individual semiconductor chip packages is not particularly limited.

[0131] [Semiconductor Device] Examples of the semiconductor device on which the above-described semiconductor chip package is mounted include various semiconductor devices used in electric products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, and airplanes, etc.).

Examples

[0132] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0133] <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 further 500 mL of N-methyl-2-pyrrolidone was placed in the separable flask and stirred at room temperature. Further, 20.0 g of 4,4'-diaminophenyl oxide (ODA) was added to the separable flask, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 40 °C, and polymerization was carried out for 20 hours.

[0134] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80 °C, and stirred for 10 hours. The obtained reaction solution was brought to 40 °C, 18.1 g of acrylic acid chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added, and the mixture was stirred for 3 hours.

[0135] Next, the obtained reaction solution was dropped into 6 L of ultrapure water, and the polyimide precursor A-1 was precipitated for purification. After the purified polyimide precursor A-1 was filtered off, it was dried under heating at 80 °C in a vacuum dryer to obtain 70 g of a polyimide precursor A-1 having the following structure. When the weight average molecular weight of the polyimide precursor A-1 was measured by gel permeation chromatography (in terms of standard polystyrene conversion), it was 40,000.

[0136] [Chemical formula]

[0137] <Synthesis Example 2: Synthesis of Polyimide Precursor A-2> 29.4 g of 3,3’,4,4’-biphenyltetracarboxylic dianhydride (sBPDA) was placed in a 2 L separable flask, and 500 mL of N-methyl-2-pyrrolidone was added to the separable flask and stirred at room temperature. Further, 41.0 g of 2,2’-bis(4-aminophenoxyphenyl)propane (BAPP) was added to the separable flask, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 40 °C, and polymerization was carried out for 20 hours.

[0138] Next, 1.12 g of potassium hydroxide was added to the reaction solution and stirred at room temperature, 8.8 g of ethylene carbonate was added, and at the same time, the separable flask was heated in an oil bath until the internal temperature reached 80 °C, and stirring was carried out for 10 hours. The obtained reaction solution was brought to 40 °C, 18.1 g of acryloyl chloride, 0.5 g of dimethylaminopyridine, and 20 g of triethylamine were added, and stirring was carried out for 3 hours.

[0139] Next, the obtained reaction solution was dropped into 6 L of ultrapure water to precipitate the polyimide precursor A-2 for purification. After filtering off the purified polyimide precursor A-2, it was dried by vacuum drying under heating at 80 °C to obtain 65 g of a polymer A-2 having the following structure. When the weight average molecular weight of the polyimide precursor A-2 was measured by gel permeation chromatography (in terms of standard polystyrene), it was 50,000.

[0140]

Chemical formula

[0141] <Preparation of photosensitive resin composition> According to the compounding amounts (unit: parts by mass) in the following table, each component was dissolved in 280 parts by mass of the solvent γ-butyrolactone (GBL) to prepare each photosensitive resin composition. In the table, the content of component (A) and the content of component (D) represent the contents when the non-volatile components of the photosensitive resin composition are 100% by mass.

[0142]

Table 1

[0143] The 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: Compound represented by the following structural formula [Chemical formula] · C-1: Compound represented by the following structure (Irgacure - OX02: manufactured by BASF) [Chemical formula] · D-1: Nitro resin coumarone H-100, manufactured by Nittosei Chemical Co., Ltd. · D-2: Nitro resin coumarone V-120S, manufactured by Nittosei Chemical Co., Ltd. · D-3: Nitro resin coumarone V-120, manufactured by Nittosei Chemical Co., Ltd. · E-1: Compound represented by the following structural formula [Chemical formula]

[0144] [Evaluation of limit resolution] Copper plating was laminated on a silicon wafer with a film thickness of 10 μm, and each of the above photosensitive resin compositions was applied onto a substrate that had been roughened with a 1% hydrochloric acid aqueous solution for 10 seconds at a rotation speed suitable for a film thickness of 25 μm using a spin coater, and then heated on a hot plate at 120 °C for 5 minutes to form a photosensitive resin composition layer. This is referred to as a laminate.

[0145] The produced laminate was exposed to ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 ). The exposure dose was set to the optimum value in the range from 50 mJ / cm 2 to 1000 mJ / cm 2 . As the exposure pattern, a quartz glass mask for drawing round holes (vias) with apertures of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm was used.

[0146] Next, spray development was performed on the entire surface of the photosensitive resin composition layer on the laminate with cyclopentanone as a developer at a spray pressure of 0.2 MPa for an optimal time between 30 seconds and 200 seconds. Subsequently, 2-methoxy-1-methylethyl acetate (PGMEA) was spray rinsed at a spray pressure of 0.2 MPa for 30 seconds. Further, heat treatment was carried out at 200 °C for 120 minutes to cure the photosensitive resin composition layer.

[0147] The diameters of the bottoms of vias with opening sizes of 10 μm, 15 μm, 20 μm, 25 μm, and 30 μm of the exposure pattern were observed (magnification 1000 times) and measured by SEM. The minimum size that could be opened was defined as the limit resolution.

[0148] <Evaluation of Dielectric Properties (Dielectric Constant, Dissipation Factor)> The photosensitive resin composition formulated with the composition in the above table was coated on the peeled PET film to a film thickness of 140 μm using a blade. After heating this solution on the PET at 80 °C for 20 minutes using a heating machine, the photosensitive resin composition layer film was peeled from the PET film, and the photosensitive resin composition layer film was attached to a metal frame using a heat-resistant tape. Further curing was carried out at 250 °C for 2 hours to prepare a film for physical property measurement.

[0149] Test pieces with a width of 2 mm and a length of 80 mm were cut from the film for physical property measurement. For the cut test pieces, the dissipation factor and dielectric constant were measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23 °C by the cavity resonance perturbation method using a measuring device "HP8362B" manufactured by Agilent Technologies.

[0150]

Table 2

[0151] In Examples 1 to 6, a cured product excellent in ultimate resolution and excellent in dielectric properties could be obtained. On the other hand, Comparative Example 1 not containing the component (D) did not have satisfactory ultimate resolution. In addition, in Examples 1 to 6, even when the component (E) was not contained, although there was a difference in degree, it was confirmed that by increasing the exposure amount, the same results as those of the above examples were achieved.

Claims

1. (A) a polyimide precursor, (B) a crosslinking agent, (C) a photo radical generator, and (D) a coumarone-indene resin, A photosensitive resin composition containing the same.

2. The photosensitive resin composition according to claim 1, further containing (E) a sensitizer.

3. The photosensitive resin composition according to claim 1 or 2, wherein the content of component (D) is 1% by mass or more and 10% by mass or less when the non-volatile components of the photosensitive resin composition are 100% by mass.

4. The photosensitive resin composition 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 components of the photosensitive resin composition are 100% by mass.

5. A photosensitive film in which a photosensitive resin composition layer composed of the photosensitive resin composition according to any one of claims 1 to 4 is formed on a support.

6. A semiconductor package substrate including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of claims 1 to 4.

7. A semiconductor device including the semiconductor package substrate according to claim 6.

8. 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 actinic rays; A method for manufacturing a semiconductor package substrate, including a step of developing the photosensitive resin composition layer.

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