Photosensitive resin composition

Abstract

To provide a photosensitive resin composition or the like which can obtain a cured product having excellent limiting resolution and excellent dielectric properties.SOLUTION: There is provided a photosensitive resin composition comprising (A) a polyimide precursor having a structural unit represented by the formula (A-1), (B) a difunctional crosslinking agent, (C) a trifunctional or higher crosslinking agent and (D) a photoradical generator, wherein when the total number of R1 and R2 groups in formula (A-1) contained in one whole molecule of the component (A) is defined as 1, a ratio in which R1 and R2 contain an unsaturated group is defined as A, the number of mass parts of the component (B) contained in the photosensitive resin composition is defined as b and the number of mass parts of the component (C) contained in the photosensitive resin composition is defined as c and B=b / (b+c) is defined, the relation of 0.2≤A×B≤0.55 is satisfied.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, and further to a photosensitive film, a semiconductor package substrate, and a semiconductor device obtained using the photosensitive resin composition. [Background technology]

[0002] Conventionally, polyimide resins, which have excellent heat resistance and insulating properties, have been used for insulating layers, etc. of semiconductor devices. Furthermore, since polyimide resins have low solubility in solvents, they are sometimes used in photosensitive resin compositions in the form of polyimide precursors, and after forming insulating layers, etc., the polyimide precursors are cyclized to form insulating layers (e.g., Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 6-80776 [Patent Document 2] Patent No. 6190805 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, with the increasing speed and capacity of communication in communication devices, there has been a demand for photosensitive resin compositions used in semiconductor package substrates for communication devices to have excellent resolution as well as excellent dielectric properties, such as low dielectric constant and dielectric loss tangent of the cured product.

[0005] The present invention has been made in view of the above-mentioned problems, and aims to provide a photosensitive resin composition that can give a cured product that is excellent in limiting resolution and dielectric properties, and a photosensitive film, a semiconductor package substrate, and a semiconductor device that are obtained using the photosensitive resin composition. [Means for solving the problem]

[0006]

[0003] Conventionally, from the viewpoint of improving photocurability, it has been considered preferable for a polyimide precursor to have more groups, such as groups represented by formula (A-2), that can undergo polymerization by radicals generated by exposure. However, the present inventors have found that, although photocurability is improved when there are more groups represented by formula (A-2), the dielectric properties of the cured product are poor. The present inventors have found that by using a photosensitive resin composition in which the product of the proportion of groups represented by formula (A-2) in the polyimide precursor and the quantitative ratio of component (B) out of two crosslinking agents, components (B) and (C), is adjusted to fall within a specified range, a cured product having excellent limiting resolution and excellent dielectric properties can be obtained, leading to the completion of the present invention.

[0007] That is, the present invention includes the following. [1] (A) a polyimide precursor having a structural unit represented by the following formula (A-1): (B) a crosslinking agent having two ethylenically unsaturated bonds and a divalent aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent; (C) a trifunctional or higher functional crosslinker, and (D) a photoradical generator, A photosensitive resin composition comprising: R in formula (A-1) contained in the entire molecule of component (A) 1 and R 2 When the total number of 1 and R 2 represents the group represented by formula (A-2), and A is When the number of parts by mass of the component (B) contained in the photosensitive resin composition is b, and the number of parts by mass of the component (C) contained in the photosensitive resin composition is c, and B = b / (b + c), A photosensitive resin composition that satisfies the relationship 0.2≦A×B≦0.55. [ka] (In formula (A-1), X1 represents a tetravalent organic group, Y1 represents a divalent organic group, and R 1 and R 2each independently represents a hydrogen atom, an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2), and n represents an integer of 2 to 200. [ka] (In formula (A-2), R 3 ~R 5 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10. [2] The photosensitive resin composition according to [1], wherein the relationship 0.8≦a / (a+b+c)≦0.9 is satisfied, where a is the number of parts by mass of the component (A) contained in the photosensitive resin composition, b is the number of parts by mass of the component (B) contained in the photosensitive resin composition, and c is the number of parts by mass of the component (C) contained in the photosensitive resin composition. [3] In formula (A-1), R 1 and R 2 each independently represents an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2): [4] In formula (A-1), R 1 and R 2 The photosensitive resin composition according to any one of [1] to [3], wherein the monovalent aliphatic hydrocarbon group, which may contain a hetero atom, is represented by the formula: [5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of component (A) is 60% by mass or more and 90% by mass or less, when the total non-volatile components of the photosensitive resin composition is 100% by mass. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the content of component (B) is 1% by mass or more and 25% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass. [7] The photosensitive resin composition according to any one of [1] to [6], wherein the content of component (C) is 0.5% by mass or more and 10% by mass or less, when the total non-volatile components of the photosensitive resin composition is 100% by mass. [8] The photosensitive resin composition according to any one of [1] to [7], further comprising (D) a photopolymerization initiator. [9] The photosensitive resin composition according to any one of [1] to [8], wherein the photosensitive resin composition has a dielectric loss tangent of 0.02 or less after being thermally cured at 180°C for 2 hours.

[10] A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of [1] to [9].

[11] 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 [9].

[12] A semiconductor device comprising the semiconductor package substrate according to

[11] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a photosensitive resin composition that can give a cured product that has excellent limiting resolution and excellent dielectric properties, and a photosensitive film, a semiconductor package substrate, and a semiconductor device that are obtained using the photosensitive resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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 below. In the following description, "dielectric constant" means "relative dielectric constant" unless otherwise specified.

[0010] [Photosensitive resin composition] The photosensitive resin composition of the present invention contains (A) a polyimide precursor having a structural unit represented by formula (A-1), (B) a crosslinking agent having two ethylenically unsaturated bonds and a divalent aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent, and (C) a trifunctional or higher functional crosslinking agent, and wherein R in formula (A-1) is contained in the entire molecule of component (A). 1 and R 2 When the total number of 1 and R 2where A is the proportion of groups represented by formula (A-2), b is the number of parts by mass of component (B) contained in the photosensitive resin composition, and c is the number of parts by mass of component (C) contained in the photosensitive resin composition, and B = b / (b + c), the relationship 0.2 ≦ A × B ≦ 0.55 is satisfied. Such a photosensitive resin composition provides a cured product with excellent limiting resolution and dielectric properties. [ka] (In formula (A-1), X1 each independently represents a tetravalent organic group, Y1 each independently represents a divalent organic group, R 1 and R 2 each independently represents a hydrogen atom, an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2), and n represents an integer of 5 to 200. [ka] (In formula (A-2), R 3 ~R 5 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[0011] The photosensitive resin composition may further contain optional components in combination with the components (A) to (C). Examples of optional components include (D) a photopolymerization initiator, (E) a sensitizer, (F) other additives, and (G) a solvent. Each component contained in the photosensitive resin composition will be described in detail below. The photosensitive resin composition of the present invention is suitable as a negative-type photosensitive resin composition.

[0012] <(A) Polyimide precursor having a structural unit represented by formula (A-1)> The photosensitive resin composition contains, as component (A), a polyimide precursor having a structural unit represented by formula (A-1). By incorporating component (A) into the photosensitive resin composition, a cured product having excellent limiting resolution and dielectric properties can be obtained. Component (A) may be used alone or in combination of two or more. Component (A) has a structural unit represented by the following formula (A-1): [ka] (In formula (A-1), X1 each independently represents a tetravalent organic group, Y1 each independently represents a divalent organic group, R 1 and R 2 each independently represents a hydrogen atom, an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2), and n represents an integer of 5 to 200. [ka] (In formula (A-2), R 3 ~R 5 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[0013] In formula (A-1), X1 each independently represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group having 6 to 40 carbon atoms. Examples of the tetravalent organic group having 6 to 40 carbon atoms include -COOR 11 Group and -COOR 12 an aromatic group in which the -CONH- group and the -CONH- group are in the ortho position relative to each other, or an alicyclic aliphatic group (R 11 and R 12 is R in formula (A-1) 1 and R 2 It is the same as the above.) Examples of such groups include groups (a3-1) to (a3-12). Among them, X1 is preferably a tetravalent organic group exemplified below, and more preferably a group (a3-5). In the formula, * represents a bond. [ka]

[0014] In formula (A-1), Y1 each independently represents a divalent organic group. The divalent organic group preferably has an aromatic ring. The divalent organic group may be a divalent organic group having an indane skeleton, or a divalent organic group having an aromatic ring in addition to the indane skeleton. Examples of the divalent organic group include groups (a4-1) to (a4-20) exemplified below, and a group combining two or more of the groups (a4-1) to (a4-20) may also be used as the divalent organic group. Among these, the group (a4-2) is preferred as Y1. In the formula, * represents a bond. [ka] [ka] [ka]

[0015] R in formula (A-1) 1 and R 2 R in formula (A-1) each independently represents a hydrogen atom, an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by formula (A-2). 1 and R 2 preferably each independently represents an allyl group, a monovalent aliphatic hydrocarbon group which may contain a hetero atom, or a group represented by formula (A-2). [ka] (In formula (A-2), R 3 ~R 5 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

[0016] The monovalent aliphatic hydrocarbon group, which may contain a heteroatom, may be either a monovalent saturated aliphatic hydrocarbon group or a monovalent unsaturated aliphatic hydrocarbon group, with a monovalent saturated aliphatic hydrocarbon group being preferred. The monovalent aliphatic hydrocarbon group may be a chain hydrocarbon group, a cyclic hydrocarbon group (i.e., an alicyclic hydrocarbon group), or a combination thereof. Furthermore, the chain hydrocarbon group may be either linear or branched. The number of carbon atoms in the monovalent aliphatic hydrocarbon group is preferably 1 or more, more preferably 4 or more, even more preferably 5 or more or 6 or more, and preferably 20 or less, more preferably 15 or less, even more preferably 10 or less or 7 or less. Examples of monovalent aliphatic hydrocarbon groups include alkyl groups.

[0017] The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 or more, more preferably 4 or more, even more preferably 5 or more, or 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 3,7-dimethyloctyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, and a cyclohexyl group.

[0018] The monovalent aliphatic hydrocarbon group may contain a heteroatom. Examples of heteroatoms include an oxygen atom, a sulfur atom, and -NH-. The group may have one heteroatom or two or more heteroatoms. When the group has two or more heteroatoms, the heteroatoms may be the same or different.

[0019] R in formula (A-2) 3 ~R 5each 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, and a 2-propyl group, with a methyl group being preferred.

[0020] 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.

[0021] Among them, in formula (A-2), R 3 and R 5 preferably represents a hydrogen atom, and R 4 preferably represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably represents an alkyl group having 1 to 3 carbon atoms, and even more preferably represents a methyl group.

[0022] R in formula (A-1) contained in the entire molecule of component (A) 1 and R 2 When the total number of 1 and R 2 The proportion A of the group represented by formula (A-2) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.25 or more, and is preferably 1, more preferably 1 or less, even more preferably 0.9 or less, 0.8 or less, or 0.7 or less. The proportion A can be determined from the amount charged when synthesizing component (A). By adjusting the proportion A within this range, it is possible to improve photocurability and reduce the dielectric loss tangent of the cured product.

[0023] R in formula (A-1) contained in the entire molecule of component (A) 1 and R 2 When the total number of 1 and R 2The proportion A' in which represents a hydrogen atom, an allyl group, and a monovalent aliphatic hydrocarbon group which may contain a heteroatom is preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.75 or less, and is preferably 0, more preferably 0 or more, and even more preferably 0.1 or more, 0.2 or more, or 0.3 or more. a By adjusting the viscosity to within this range, it is possible to improve the photocurability and reduce the dielectric loss tangent of the cured product.

[0024] R in formula (A-1) contained in the entire molecule of component (A) 1 and R 2 When the total number of 1 and R 2 represents an allyl group and a monovalent aliphatic hydrocarbon group which may contain a heteroatom; a1 is preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.75 or less, and is preferably 0, more preferably 0 or more, even more preferably 0.1 or more, 0.2 or more, or 0.3 or more. a1 By adjusting the viscosity to within this range, it is possible to improve the photocurability and reduce the dielectric loss tangent of the cured product.

[0025] In formula (A-1), n ​​represents an integer of 5 to 200, preferably an integer of 5 to 180, more preferably an integer of 5 to 150, still more preferably an integer of 5 to 100, or an integer of 5 to 70.

[0026] Specific examples of the component (A) include compounds containing the repeating units (Aa-1) to (Aa-10) below. However, the component (A) is not limited to these specific examples. In each formula, n represents an integer of 5 to 200, and the proportion of R groups represented by formula (A-2) is 0.1 or more and 0.9 or less. * represents a bond. [ka] [ka] [ka] [ka]

[0027] Component (A) can usually be obtained by reacting a tetracarboxylic dianhydride, a diamine compound, and an alcohol. Specific production methods for component (A) include those described in JP-A-2015-209461 and JP-A-2015-214680.

[0028] The weight average molecular weight of component (A) is preferably 3,000 or more, more preferably 6,000 or more, and even more preferably 9,000 or more, and is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent value.

[0029] The content of component (A), when the non-volatile components of the photosensitive resin composition are taken as 100% by mass, is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 75% by mass or more, and is preferably 90% by mass or less, more preferably 88% by mass or less, even more preferably 86% by mass or less.

[0030] 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 taken as 100 mass %, unless otherwise specified.

[0031] When the number of parts by mass of the component (A) contained in the photosensitive resin composition is represented by a, a is preferably 60 or more, more preferably 70 or more, even more preferably 75 or more, and is preferably 90, more preferably 88 or less, even more preferably 86 or less.

[0032] <(B) Crosslinking Agent Having Two Ethylenically Unsaturated Bonds and a Divalent Aliphatic Hydrocarbon Group Having 8 or More Carbon Atoms, Which May Have a Substitute> The photosensitive resin composition contains, as component (B), a crosslinking agent having two ethylenically unsaturated bonds and a divalent aliphatic hydrocarbon group having 8 or more carbon atoms, which may have a substituent. By using component (B) and component (C), described below, as crosslinking agents, and adjusting the amount of component (B) in the crosslinking agent to a predetermined ratio while adjusting the product of the proportion of the group represented by formula (A-2) in component (A) and the above ratio to fall within a predetermined range, it is possible to obtain a cured product with excellent limiting resolution and dielectric properties. Component (B) may be used alone or in combination with two or more. Component (B) does not include those corresponding to component (A) described above.

[0033] Component (B) may be a compound having two ethylenically unsaturated bonds and a divalent aliphatic hydrocarbon group having 8 or more carbon atoms. The ethylenically unsaturated bond represents a carbon-carbon double bond. Therefore, component (B) may contain a group having an ethylenically unsaturated bond (hereinafter, referred to as an "ethylenically unsaturated group" as appropriate). The ethylenically unsaturated group is typically a monovalent group, such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, or a (meth)acryloyl group. From the viewpoint of photoradical polymerization reactivity, a (meth)acryloyl group or a phenylethynyl group is preferred, with a (meth)acryloyl group being particularly preferred. Because component (B) contains an ethylenically unsaturated bond, it is photoradical polymerizable. Furthermore, the two ethylenically unsaturated groups in component (B) may be the same or different.

[0034] From the viewpoint of reducing the dielectric loss tangent, the number of carbon atoms in the divalent aliphatic hydrocarbon group having 8 or more carbon atoms is 8 or more, and preferably 9 or more. From the viewpoint of reducing the dielectric loss tangent, the upper limit is preferably 20 or less, more preferably 15 or less, and even more preferably 12 or less.

[0035] Examples of divalent aliphatic hydrocarbon groups having 8 or more carbon atoms include alkylene groups having 8 or more carbon atoms, alkenylene groups having 8 or more carbon atoms, and alkynylene groups having 8 or more carbon atoms, and alkylene groups having 8 or more carbon atoms are preferred.

[0036] Examples of alkylene groups having 8 or more carbon atoms include an octylene group, a nonylene group, a decylene group, an undecylene group, and a dodecylene group. Examples of alkenylene groups having 8 or more carbon atoms include an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, and a dodecenylene group. Examples of alkynylene groups having 8 or more carbon atoms include an octenylene group, a nonenylene group, a decenylene group, an undecenylene group, and a dodecenylene group.

[0037] The divalent aliphatic hydrocarbon group having 8 or more carbon atoms may have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom; a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isopropyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, or a propoxy group; a hydroxy group; and a halogen-substituted alkyl group such as a trifluoromethyl group, with a halogen atom being preferred. The above-mentioned substituents may further have a substituent (hereinafter sometimes referred to as a "secondary substituent"). The substituent may be contained alone or in combination of two or more types.

[0038] The component (B) is preferably a compound represented by the following formula (B-1). [ka] (In the formula, R 1b and R 2b each independently represents a hydrogen atom or a methyl group, and nb represents an integer of 8 to 20.

[0039] R 1b and R 2bR each independently represents a hydrogen atom or a methyl group, and a methyl group is preferred. 1b and R 2b At least one of the groups is preferably a methyl group, and more preferably both are methyl groups.

[0040] nb represents an integer of 8 or more and 20 or less, and is preferably 9 or more. The upper limit is preferably 15 or less, and more preferably 12 or less.

[0041] Specific examples of the component (B) include the following compounds (B1) to (B3): However, the component (B) is not limited to these specific examples. [ka]

[0042] Component (B) may be a commercially available product, such as "NOD-N" or "DOD-N" manufactured by Shin-Nakamura Chemical Co., Ltd.

[0043] The content of the (B) component is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, per 100 parts by mass of the (A) component, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0044] The content of component (B) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass.

[0045] When the number of parts by mass of the component (B) contained in the photosensitive resin composition is designated as b, b is preferably 1 or more, more preferably 3 or more, and even more preferably 4 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0046] Furthermore, a / b is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, and is preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less.

[0047] <(C) Trifunctional or higher crosslinking agent> The photosensitive resin composition contains a trifunctional or higher functional crosslinking agent (C) as component (C). However, component (C) does not include components (A) and (B) described above. By using components (C) and (B) as crosslinking agents and adjusting the amount of component (B) in the crosslinking agent to a predetermined ratio while adjusting the product of the proportion of the group represented by formula (A-2) in component (A) and the above ratio to fall within a predetermined range, it is possible to obtain a cured product with excellent limiting resolution and dielectric properties. Component (C) may be used alone or in combination of two or more.

[0048] Component (C) is a crosslinking agent having three or more functional groups, and a compound capable of causing a crosslinking reaction upon exposure can be used. Examples of functional groups include groups having an ethylenically unsaturated bond (ethylenically unsaturated groups), and the groups having an ethylenically unsaturated bond are as described above. The preferred ethylenically unsaturated groups in component (C) are the same as those in component (B), and from the viewpoint of reactivity in photoradical polymerization, (meth)acryloyl groups and phenylethynyl groups are preferred, with (meth)acryloyl groups being particularly preferred.

[0049] The number of functional groups per molecule of component (C) is 3 or more, preferably 4 or more, and preferably 8 or less, more preferably 6 or less, and even more preferably 5 or less. The three or more functional groups contained in component (C) may be the same or different.

[0050] The component (C) is preferably a compound represented by the following general formula (C-1). [ka] (In the formula, R 1ceach independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms; Z 1c 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; A 1c represents a linear, cyclic, or branched organic group having 1 to 10 carbon atoms and a valence of nc, where nc is a positive integer of 3 to 6.

[0051] R 1c are each independently 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, a s-butyl group, and a t-butyl group. Among these, R 1c is preferably a hydrogen atom or a methyl group.

[0052] Z 1c 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 preferred, and a linear or branched alkylene group having 1 to 6 carbon atoms is more preferred. Examples of such alkylene groups include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, with a methylene group being preferred. The alkylene group may also be an oxyalkylene group containing an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, c1 represents an integer of 1 to 20, c2 represents an integer of 1 to 10, c3 represents an integer of 1 to 19, and c4 represents an integer of 1 to 9. [ka]

[0053] 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. The arylene group may also contain an oxygen atom, and specific examples of such groups include those shown below. In the formula, "*" represents a bond, and c5 represents an integer of 1 to 3. [ka]

[0054] As the linear or branched alkenylene group having 2 to 20 carbon atoms which may contain an oxygen atom, a linear or branched alkenylene group having 2 to 10 carbon atoms is preferred, and a linear or branched alkenylene group having 2 to 6 carbon atoms is more preferred. Examples of such alkenylene groups include ethenylene, propenylene, butenylene, pentenylene, and hexenylene. The alkenylene group may also 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 c6 represents an integer of 1 to 10. The alkenylene group is preferably a propenylene group. [ka]

[0055] Among them, Z 1c As the alkyl group, a linear or branched alkylene group having 1 to 20 carbon atoms which may contain an oxygen atom is preferred, and a methylene group is more preferred.

[0056] A 1crepresents a linear, cyclic, or branched nc-valent organic group having 1 to 10 carbon atoms. Examples of the nc-valent organic group include an nc-valent hydrocarbon group which may contain an oxygen atom, an nc-valent group derived from bisphenol, an nc-valent group derived from fluorene, an nc-valent group derived from tricyclodecane, or an nc-valent group derived from an isocyanuric group. Examples of the nc-valent hydrocarbon group which may contain an oxygen atom include an nc-valent aliphatic hydrocarbon group which may contain an oxygen atom, and an nc-valent aromatic hydrocarbon group which may contain an oxygen atom, with an nc-valent aliphatic hydrocarbon group which may contain an oxygen atom being preferred. A 1c Specific examples of the group represented by include the following: In the formula, "*" represents a bond. [ka]

[0057] nc represents a positive integer of 3 to 6, preferably a positive integer of 3 to 5, more preferably 3 or 4, and even more preferably 3.

[0058] The component (C) is preferably a compound represented by the following general formula (C-2). [ka] (In the formula, R 2c each independently represents a hydrogen atom or a methyl group.

[0059] Specific examples of the component (C) include the following compounds (CL-1) to (CL-6). However, the component (C) is not limited to these specific examples. In the formula, p, q, and r are the same as nc in formula (C-1). [ka]

[0060] Component (C) can be a commercially available product, such as "TMPT," "A-TMPT," "A-TMPT-9EO," "A-GLY-3E," and "A-9300" manufactured by Shin-Nakamura Chemical Co., Ltd.; "DPHA," "EBECRYL 40," "EBECRYL 50," and "EBECRYL 140" manufactured by Daicel-Allnex Corporation.

[0061] The content of component (C) is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and even more preferably 2 parts by mass or more, per 100 parts by mass of component (A), and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0062] The content of component (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass.

[0063] When the number of parts by mass of component (C) contained in the photosensitive resin composition is designated as c, c is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more, and is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.

[0064] B=b / (b+c) is preferably 0.5 or more, more preferably 0.55 or more, even more preferably 0.6 or more, and is preferably 1 or less, more preferably 0.9 or less, even more preferably 0.8 or less.

[0065] A×B is 0.2 or more, preferably 0.25 or more, and more preferably 0.3 or more. The upper limit is 0.55 or less, preferably 0.53 or less, and more preferably 0.51 or less, or 0.5 or less. By adjusting the amounts of components (A) to (C) so that A×B falls within this range, it is possible to obtain a cured product with a low dielectric loss tangent and excellent limiting resolution.

[0066] a / (a+b+c) is preferably 0.8 or greater, more preferably 0.81 or greater, and even more preferably 0.82 or greater, and is preferably 0.9 or less, more preferably 0.89 or less, and even more preferably 0.88 or less. By adjusting the amounts of components (A) to (C) so that a / (a+b+c) falls within this range, it is possible to obtain a cured product with a low dielectric loss tangent and excellent limiting resolution.

[0067] b / c is preferably 0.1 or more, more preferably 0.5 or more, even more preferably 1 or more, and is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less.

[0068] Furthermore, a / c is preferably 5 or more, more preferably 10 or more, and even more preferably 15 or more, and is preferably 55 or less, more preferably 50 or less, and even more preferably 45 or less.

[0069] <(D) Photopolymerization initiator> The photosensitive resin composition may contain a (D) photopolymerization initiator as component (D). However, component (D) excludes components (A) to (C). Component (D) may be a compound capable of generating radicals upon exposure to actinic rays. Component (D) may be used alone or in combination of two or more.

[0070] Examples of the component (D) include oxime ester-based photopolymerization initiators, aminoketone-based photopolymerization initiators, acylphosphine-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, benzoin-based photopolymerization initiators, and benzyl ketal-based photopolymerization initiators. Of these, oxime ester-based photopolymerization initiators are preferred.

[0071] Examples of the oxime ester photopolymerization initiator include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]octan-1-one (OXE01), [1-[9-ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate (OXE02), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and the like.

[0072] Examples of the aminoketone photopolymerization initiator include α-aminoketone photopolymerization initiators such as 2-methyl-1-phenyl-2-morpholinopropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-methyl-1-(4-hexylphenyl)-2-morpholinopropan-1-one, 2-ethyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, 2-(dimethylamino)-2-(4-methylphenylmethyl)-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-(9,9-dibutylfluoren-2-yl)-2-morpholinopropan-1-one.

[0073] Examples of the acylphosphine photopolymerization initiator include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, and polyoxyethylene glycerin ether tris[phenyl(2,4,6-trimethylbenzoyl)phosphinate] (Polymeric TPO-L).

[0074] Examples of the α-hydroxyketone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropanone, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one.

[0075] Examples of the benzoin-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0076] An example of the benzyl ketal photopolymerization initiator is 2,2-dimethoxy-2-phenylacetophenone.

[0077] Component (D) may be a commercially available product. Specific examples of commercially available products of component (D) include "Omnirad907," "Omnirad369," "Omnirad379," "Omnirad379EG," "Omnirad819," and "OmniradTPO" manufactured by IGM; "IrgacureTPO," "Irgacure OXE-01," and "Irgacure OXE-02" manufactured by BASF; and "N-1919" manufactured by ADEKA Corporation.

[0078] The content of the (D) component is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the (A) component, and is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less.

[0079] The content of component (D) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, when the non-volatile components of the photosensitive resin composition are taken as 100% by mass.

[0080] <(E) Sensitizer> The photosensitive resin composition may contain a sensitizer (E) as an optional component. By including a sensitizer (E) in the photosensitive resin composition, it is possible to improve the photosensitivity of the photosensitive resin composition. The component (E) may be used alone or in combination of two or more. In addition, the component (E) does not include components (A) to (D) described above.

[0081] The component (E) can be 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, and 4-morpholinobenzophenone; cyclic alkanes such as 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, and 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone; chalcones such as 4,4'-bis(dimethylamino)chalcone and 4,4'-bis(diethylamino)chalcone; indanones such as p-dimethylaminocinnamylidene indanone and p-dimethylaminobenzylidene indanone; thiazoles such as 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, and 2-(p-dimethylaminophenylvinylene)isonaphthothiazole; acetones such as 1,3-bis(4'-dimethylaminobenzal)acetone and 1,3-bis(4'-diethylaminobenzal)acetone; 3,3'-carbonyl-bis(7-diethylaminobenzal)acetone; coumarins such as 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, and 3-ethoxycarbonyl-7-diethylaminocoumarin; N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, isoamyl dimethylaminobenzoate, diethanolamine; amines such as isoamyl methylaminobenzoate; heterocyclic compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 1-phenyl-5-mercaptotetrazole, and 1-p-hydroxyphenyl-5-mercaptotetrazole; and styrenes such as 2-(p-dimethylaminobenzoyl)styrene.

[0082] The content of component (E) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more, per 100 parts by mass of component (A), and is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less.

[0083] The content of component (E) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, and is preferably 8% by mass or less, more preferably 6% by mass or less, and even more preferably 4% by mass or less, when the total non-volatile components of the photosensitive resin composition is taken as 100% by mass.

[0084] <(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. Examples of (F) other additives include thermal radical initiators, 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, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, thickeners such as bentone and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoamers, flame retardants such as epoxy resins, antimony compounds, phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters, and thermosetting resins such as phenolic curing agents and cyanate ester-based curing agents.

[0085] <(G) Solvent> The photosensitive resin composition may contain a (G) solvent as an optional component in combination with the non-volatile components (A) to (F) described above. The (G) solvent is preferably a volatile component that can uniformly dissolve at least one of the (A) to (C) components and the optional (D) to (F) components. The (G) component may be used alone or in combination of two or more.

[0086] 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, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and triethylene glycol dimethyl ether; ketone compounds having 2 to 6 carbon atoms, such as methyl ethyl ketone, methyl isobutyl ketone, acetone, cyclopentanone, and methyl ethyl ketone; saturated hydrocarbon compounds having 5 to 10 carbon atoms, such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; and benzene, toluene, xylene, mesitylene, pyridine, anisole, and tetraethylene glycol dimethyl ether. aromatic hydrocarbon compounds having 6 to 10 carbon atoms, such as thoralin; ester compounds having 3 to 9 carbon atoms, such as methyl acetate, ethyl acetate, γ-butyrolactone, α-acetyl-γ-butyrolactone, ethyl acetate, ethyl lactate, butyl lactate, 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 N-ethyl-2-pyrrolidone, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-methylpyrrolidone, 3-methoxy-N,N-dimethylpropanamide, and N-methyl-2-pyrrolidone; phosphorus-containing compounds, such as hexamethylphosphoramide; and sulfur-containing compounds, such as dimethyl sulfoxide.

[0087] The content of the (G) component, when the entire photosensitive resin composition including the (G) component is taken as 100% by mass, is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, and is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.

[0088] The photosensitive resin composition can be produced by mixing the essential components (A) to (C) described above, and optionally mixing the optional components (D) to (G) described above, and kneading or stirring the mixture, if necessary, using a kneading device such as a triple roll mill, a ball mill, a bead mill, or a sand mill, or a stirring device such as a super mixer or a planetary mixer.

[0089] <Physical properties and applications of photosensitive resin compositions> The photosensitive resin composition exhibits excellent limiting resolution. For example, exposure and development are performed using a mask that draws circular holes with opening diameters of 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern. In this case, the limiting resolution, which is the minimum size that can be opened, is preferably less than 25 μm, more preferably less than 18 μm. The limiting resolution can be measured according to the method described in the Examples below.

[0090] A cured product obtained by thermally curing a photosensitive resin composition at 180°C for 2 hours exhibits the characteristic of a low dielectric constant (Dk). The dielectric constant at 23°C is preferably 4.5 or less, more preferably 4 or less, and even more preferably 3.5 or less. The lower limit is not particularly limited, but may be 1 or more, for example. The dielectric constant can be measured according to the method described in the Examples below.

[0091] A cured product obtained by thermally curing a photosensitive resin composition at 180°C for 2 hours exhibits the characteristic of a low dielectric loss tangent (Df). The dielectric loss tangent at 23°C is preferably 0.02 or less, more preferably 0.015 or less, and even more preferably 0.01 or less. The lower limit is not particularly limited, but may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples below.

[0092] The photosensitive resin composition of the present invention is not particularly limited in its applications, but can be used in a wide range of applications where photosensitive resin compositions are used, such as photosensitive films, insulating resin sheets such as prepregs, silicon wafers, circuit boards (for laminates, multilayer printed wiring boards, etc.), solder resists, buffer coating films, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, and component-embedding resins. Among these, photosensitive resin compositions for insulating layers of printed wiring boards (printed wiring boards in which a cured product of the photosensitive resin composition is used as an insulating layer), photosensitive resin compositions for interlayer insulating layers (printed wiring boards in which a cured product of the photosensitive resin composition is used as an interlayer insulating layer), photosensitive resin compositions for plating (printed wiring boards in which plating is formed on a cured product of the photosensitive resin composition), and photosensitive resin compositions for solder resists (printed wiring boards in which a cured product of the photosensitive resin composition is used as a solder resist), photosensitive resin compositions for rewiring formation layers of wafer-level packages (wafer-level packages in which a cured product of the photosensitive resin composition is used as a rewiring formation layer), The photosensitive resin composition can be suitably used as a photosensitive resin composition for a rewiring formation layer in a fan-out wafer-level package (a fan-out wafer-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a rewiring formation layer in a fan-out panel-level package (a fan-out panel-level package in which a cured product of the photosensitive resin composition serves as a rewiring formation layer), a photosensitive resin composition for a buffer coat (a semiconductor device in which a cured product of the photosensitive resin composition serves as a buffer coat), or a photosensitive resin composition for an insulating layer in a display (a display in which a cured product of the photosensitive resin composition serves as an insulating layer).

[0093] [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 made of the above-mentioned photosensitive resin composition. The photosensitive film may also include a support, a photosensitive resin composition layer, and a protective film in this order.

[0094] Examples of the support include polyethylene terephthalate film, polyethylene naphthalate film, polypropylene film, polyethylene film, polyvinyl alcohol film, and triacetyl acetate film, with polyethylene terephthalate film being particularly preferred.

[0095] Examples of commercially available supports include, but are not limited to, Oji Paper Co., Ltd. products under the names "Alphan MA-410" and "E-200C," Tamapoly Co., Ltd. products under the names "GF-1" and "GF-8," polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and polyethylene terephthalate films such as the PS series manufactured by Teijin Limited under the name "PS-25." These supports are preferably coated on the surface with a release agent such as a silicone coating or a non-silicone coating to facilitate removal. Examples of supports whose surfaces have been treated with such release agents 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.

[0096] 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, preferably 2 μm or more, more preferably 4 μm or more, and preferably 50 μm or less, more preferably 30 μm or less.

[0097] The photosensitive resin composition layer may be protected by a protective film. Protecting the photosensitive resin composition layer with a protective film can prevent dust from adhering to the surface of the photosensitive resin composition layer and scratches. The protective film may be made of the same material as the support. 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. The protective film is preferably one in which the adhesive strength between the photosensitive resin composition layer and the protective film is smaller than the adhesive strength between the photosensitive resin composition layer and the support.

[0098] The photosensitive film can be produced, for example, by applying the photosensitive resin composition onto a support and, if necessary, drying off the (G) solvent.

[0099] The content of 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, even more preferably 3% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, when the entire photosensitive resin composition including component (G) is taken as 100% by mass.

[0100] [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 formation layer, an interlayer insulating layer, a buffer coating film, or a solder resist.

[0101] In particular, the semiconductor package substrate of the first embodiment of the present invention can be manufactured using the above-mentioned photosensitive resin composition, and the cured product of the photosensitive resin composition is used as an insulating layer. Specifically, the manufacturing method of the 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; Contains, in this order:

[0102] <Process (I)> Methods for forming the photosensitive resin composition layer include a method in which a resin varnish containing the photosensitive resin composition is directly applied onto the circuit board, and a method in which the photosensitive film is used.

[0103] When a resin varnish containing a photosensitive resin composition is applied directly onto a circuit board, a photosensitive resin composition layer is formed on the circuit board by drying and volatilizing component (G).

[0104] Examples of resin varnish application methods include gravure coating, microgravure coating, reverse coating, kiss reverse coating, die coating, slot die coating, lip coating, comma coating, blade coating, roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice coating, spin coating, slit coating, spray coating, dip coating, hot melt coating, bar coating, applicator coating, air knife coating, curtain flow coating, offset printing, brush coating, and full-surface printing using screen printing.

[0105] The resin varnish may be applied in several batches, in one application, or by a combination of several different methods. Among these, the die coating method is preferred because it provides excellent uniformity. Furthermore, to avoid contamination, it is preferable to carry out the application process in an environment where foreign matter is less likely to be generated, such as a clean room.

[0106] After the resin varnish is applied, it is dried, if necessary, in a hot air oven or far-infrared oven. The drying conditions are preferably 80°C to 120°C for 3 to 13 minutes. In this way, a photosensitive resin composition layer is formed on the circuit board.

[0107] Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board in which a patterned conductor layer (circuit) is formed on one or both sides of a support substrate such as those described above. Also included in the term "circuit board" is a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, in which one or both sides of the outermost layer of the multilayer printed wiring board are patterned conductor layers (circuits). The surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.

[0108] On the other hand, when a photosensitive film is used, the photosensitive resin composition layer is laminated on one or both sides of the circuit board using a vacuum laminator. In the laminating step, if the photosensitive film has a protective film, the protective film is removed, and then the photosensitive film and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressure-bonded to the circuit board while being pressurized and heated. For the photosensitive film, a method of laminating the film to the circuit board under reduced pressure by a vacuum lamination method is preferably used.

[0109] The lamination conditions are not particularly limited, but for example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the pressure-bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2), and the pressure bonding time is preferably 5 to 300 seconds, and lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0110] <Process (II)> After the photosensitive resin composition layer is provided on the circuit board, an exposure step is then performed in which actinic rays are irradiated to predetermined portions of the photosensitive resin composition layer through a mask pattern. Examples of actinic rays include ultraviolet rays, visible rays, electron beams, and X-rays, with ultraviolet rays being particularly preferred. The irradiation dose of ultraviolet rays is approximately 10 mJ / cm. 2 ~1000mJ / cm 2 There are two types of exposure methods: contact exposure, in which a mask pattern is placed in close contact with the circuit board, and non-contact exposure, in which parallel light is used for exposure without contact, and either method can be used.

[0111] In step (II), vias can be formed using a via pattern such as a round hole pattern as a 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. The lower limit is not particularly limited, but can be 0.1 μm or more, 0.5 μm or more, etc.

[0112] <Process (III)> After the exposure step, a development step is carried out in which the unexposed portions of the photosensitive resin composition layer are removed with a developer, thereby forming a pattern. The development is usually carried out by wet development.

[0113] In the case of the wet development, a developer that is safe, stable, and easy to handle is used, such as an alkaline solution, an aqueous developer, an organic solvent, etc. As the developing method, a known method such as spraying, shaking immersion, brushing, scraping, etc. is suitably adopted.

[0114] Examples of alkaline aqueous solutions 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; and alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; and aqueous solutions of organic bases that do not contain metal ions, such as tetraalkylammonium hydroxide. Of these, an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.

[0115] These alkaline aqueous solutions may contain a surfactant, an antifoaming agent, etc. to improve the development effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, more preferably in the range of 9 to 11. 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 depending on the developability of the photosensitive resin composition layer, but is preferably 20°C to 50°C.

[0116] Examples of organic solvents used as developers include acetone, ethyl acetate, alkoxyethanols having an alkoxy group having 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.

[0117] The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. The temperature of such an organic solvent can be adjusted according to the developability. Such organic solvents can be used alone or in combination of two or more. Examples of organic solvent-based developers that can be used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

[0118] In forming a pattern, two or more development methods may be used in combination as needed. Development methods include dipping, bathing, spraying, high-pressure spraying, brushing, and slapping, with the high-pressure spraying method being preferred for improving resolution. When using a spraying method, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

[0119] <Thermal curing (post-bake) process> After the completion of the step (III), a thermal curing (post-baking) step is carried out as necessary. Although the curing of the photosensitive resin composition layer may proceed in the steps (I) to (III) described above, the thermal curing step can further promote the curing of the photosensitive resin composition, thereby obtaining an insulating layer with excellent mechanical strength. Examples of the post-baking step include a heating step using a clean oven. The thermal curing atmosphere may be air or an inert gas atmosphere such as nitrogen. The heating conditions may be appropriately selected depending on the type and content of the resin component in the photosensitive resin composition, but are preferably selected within the range of 150°C to 250°C for 20 to 180 minutes, and more preferably 160°C to 230°C for 30 to 120 minutes.

[0120] <Other processes> The method for producing a semiconductor package substrate may further include a drilling step and a desmearing step after forming an insulating layer as a cured photosensitive resin composition layer. These steps may be performed according to various methods used in the production of semiconductor package substrates and known to those skilled in the art.

[0121] After forming the insulating layer, if desired, via holes or through holes are formed in the insulating layer formed on the circuit board by a drilling process. The drilling process can be performed by a known method such as a drill, a laser, or plasma, or by a combination of these methods as needed, but a drilling process using a laser such as a carbon dioxide laser or a YAG laser is preferred.

[0122] The desmearing process is a process of performing a desmear treatment. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling process. Since such smear can cause poor electrical connection, a process of removing the smear (desmearing process) is performed in this process.

[0123] The desmearing may be performed by a dry desmearing, a wet desmearing, or a combination thereof.

[0124] An example of the dry desmear treatment is a desmear treatment using plasma. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear treatment apparatuses, examples suitable for use in manufacturing semiconductor package substrates include a microwave plasma apparatus manufactured by Nissin Corporation and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

[0125] Examples of wet desmear treatments include desmear treatments using an oxidizing agent solution. When desmear treatments are performed using an oxidizing agent solution, it is preferable to perform a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent solution, and a neutralization treatment using a neutralizing solution in this order. Examples of swelling solutions include "Swelling Dip Securigance P" and "Swelling Dip Securigance SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate having via holes or the like formed therein in a swelling solution heated to 60°C to 80°C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, such as a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous sodium hydroxide solution. The oxidation treatment using an oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60°C to 80°C for 10 to 30 minutes. Commercially available alkaline permanganate aqueous solutions include, for example, "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralization treatment using a neutralizing solution is preferably carried out by immersing the substrate after oxidation treatment in the neutralizing solution at 30°C to 50°C for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and a commercially available product thereof is, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan.

[0126] 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.

[0127] In any case where the insulating layer is formed as a rewiring formation layer, an interlayer insulating layer, or a solder resist, a drilling step and a desmearing step may be performed after the thermal curing step. In addition, in the manufacturing method of a semiconductor package substrate, a plating step may be further performed.

[0128] The plating process is a process of forming a conductor layer on an insulating layer. The conductor layer may be formed by sputtering after the insulating layer is formed, or by a combination of electroless plating and electrolytic plating. Alternatively, a plating resist having a reverse pattern to the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. Subsequent pattern formation methods that can be used include, for example, subtractive methods and semi-additive methods known to those skilled in the art.

[0129] 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 manufacturing method of the semiconductor package substrate includes: (A) a step of laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (C) forming an encapsulation layer on the semiconductor chip; (D) 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 base material and the temporary fixing film have been peeled off; (F) forming a rewiring layer as a conductor layer on the rewiring formation layer; and (G) forming a solder resist layer on the rewiring layer; The method for manufacturing the semiconductor chip package also includes: (H) dicing and singulating the plurality of semiconductor chip packages into individual semiconductor chip packages; may also include:

[0130] <Process (A)> Step (A) is a step of laminating a temporary fixing film on a substrate. The lamination conditions for the substrate and the temporary fixing film are not particularly limited, but for example, the pressure-bonding temperature (lamination temperature) is preferably 70°C to 140°C, and the pressure-bonding pressure is preferably 1 kgf / cm. 2 ~11kgf / cm 2Preferably, the pressure bonding time is set to 5 to 300 seconds, and lamination is performed under reduced pressure with an air pressure of 20 mmHg or less. The lamination process may be a batch process or a continuous process using rolls. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum applicator manufactured by Nikko Materials Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi Industries Co., Ltd., and a vacuum laminator manufactured by Hitachi AIC Corporation.

[0131] Examples of the substrate include silicon wafers; glass wafers; glass substrates; metal substrates such as copper, titanium, stainless steel, and cold-rolled steel sheets (SPCC); substrates such as FR-4 substrates in which glass fibers are impregnated with epoxy resin or the like and then thermoset; and substrates made of bismaleimide triazine resins such as BT resin.

[0132] The temporary fixing film may be made of any material that can be peeled off from the semiconductor chip and can temporarily fix the semiconductor chip. Commercially available products include "Riva Alpha" manufactured by Nitto Denko Corporation.

[0133] <Process (B)> Step (B) is a step of temporarily fixing semiconductor chips on a temporary fixing film. Temporarily fixing semiconductor chips can be performed using a device such as a flip chip bonder or a die bonder. The layout and number of semiconductor chips can be appropriately set depending on 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 temporarily fixed by arranging them in a matrix of multiple rows and multiple columns.

[0134] <Process (C)> Step (C) is a step of forming an encapsulating layer on the semiconductor chip. Any insulating material can be used for the encapsulating layer, and the above-mentioned photosensitive resin composition may also be used. The encapsulating layer is usually formed by a method including a step of forming an encapsulating resin composition layer on the semiconductor chip and a step of thermally curing this resin composition layer to form the encapsulating layer.

[0135] The encapsulating resin composition layer is preferably formed by a compression molding method, in which a semiconductor chip and the encapsulating resin composition are typically placed in a mold, and pressure and, if necessary, heat are applied to the encapsulating resin composition in the mold to form an encapsulating resin composition layer that covers the semiconductor chip.

[0136] Specific operations of the compression molding method can be, for example, as follows. An upper mold and a lower mold are prepared as molds for compression molding. An encapsulating resin composition is applied to the semiconductor chip temporarily fixed on the temporary fixing film as described above. The semiconductor chip to which the encapsulating resin composition has been applied 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 together, and heat and pressure are applied to the encapsulating resin composition to perform compression molding. A known encapsulating resin composition can be used as the encapsulating resin composition.

[0137] Furthermore, specific operations 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. An encapsulating resin composition is placed on the lower mold. A semiconductor chip is attached to the upper mold together with a substrate and a temporary fixing film. Thereafter, the upper and lower molds are clamped together so that the encapsulating resin composition placed on the lower mold contacts the semiconductor chip attached to the upper mold, and heat and pressure are applied to perform compression molding.

[0138] The molding conditions vary depending on the composition of the encapsulating resin composition, and appropriate conditions can be adopted to achieve good encapsulation. For example, the mold temperature during molding is preferably a temperature at which the encapsulating resin composition exhibits excellent compression moldability, and is 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, and 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 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, and particularly preferably 20 minutes or shorter. Typically, the mold is removed after the encapsulating resin composition layer is formed. The mold may be removed before or after the encapsulating resin composition layer is thermally cured.

[0139] The compression molding method may be carried out by discharging the encapsulating resin composition filled in a cartridge into a lower mold.

[0140] <Process (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 peeling method depending on the material of the temporary fixing film. Examples of peeling methods include a method in which the temporary fixing film is heated, foamed, or expanded to peel it off. Another example of a peeling method is a method in which the temporary fixing film is irradiated with ultraviolet light through the substrate to reduce the adhesive strength of the temporary fixing film, thereby peeling it off.

[0141] In the method of peeling off the temporary fixing film by heating, foaming or expanding it, 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 peeling off the temporary fixing film by irradiating it with ultraviolet light to reduce the adhesive strength of the temporary fixing film, the irradiation dose of ultraviolet light is usually 10 mJ / cm. 2 ~1000mJ / cm 2 is.

[0142] <Process (E)> Step (E) is 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 off. The rewiring formation layer uses the photosensitive resin composition of the present invention. The method for forming the rewiring formation layer is the same as the method for forming the photosensitive resin composition layer in step (I) in the first embodiment.

[0143] When forming the rewiring formation layer, via holes may be formed in the rewiring formation layer to connect the semiconductor chip and the rewiring layer to each other.

[0144] The via hole can usually be formed by performing an exposure step in which the surface of the photosensitive resin composition layer for forming the rewiring formation layer is irradiated with actinic rays through a mask pattern, and a development step in which the non-exposed area not irradiated with actinic rays is developed and removed. The dose and irradiation time of the actinic rays can be appropriately set depending on the photosensitive resin composition layer. Examples of the exposure method include a contact exposure method in which a mask pattern is closely attached to the photosensitive resin composition layer and exposed, and a non-contact exposure method in which a mask pattern is not closely attached to the photosensitive resin composition layer and exposed using parallel rays. The actinic rays, alkaline aqueous solution, and exposure and development method are as described above.

[0145] The shape of the via hole is not particularly limited, but is generally circular (approximately circular). The top diameter of the via hole is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less, and is 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 refers to the diameter of the opening of the via hole on the surface of the rewiring formation layer.

[0146] <Process (F)> Step (F) is a step of forming a redistribution layer as a conductor layer on the redistribution formation layer. The method of forming the redistribution layer on the redistribution formation layer can be the same as the method of forming a conductor layer on an insulating layer in the first embodiment. Steps (E) and (F) may be repeated to alternately stack (build up) the redistribution layers and the redistribution formation layers.

[0147] <Process (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 for the solder resist layer. Among them, photosensitive resins and thermosetting resins are preferred from the viewpoint of ease of manufacturing a semiconductor chip package. The photosensitive resin composition of the present invention may also be used.

[0148] In step (G), bumping processing may be performed to form bumps, if necessary. The bumping processing can be performed by a method such as solder balls or solder plating. In addition, the formation of via holes in the bumping processing can be performed in the same manner as in step (E).

[0149] The method for manufacturing a semiconductor chip package may include a step (H) in addition to the steps (A) to (G). The step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages. The method for dicing the semiconductor chip packages into individual semiconductor chip packages is not particularly limited.

[0150] [Semiconductor Devices] Examples of semiconductor devices on which the above-mentioned semiconductor chip package is mounted include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, and televisions) and vehicles (e.g., motorcycles, automobiles, trains, ships, and aircraft). [Example]

[0151] The present invention will be described in more detail below using 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.

[0152] <Synthesis Example 1: Synthesis of Polyimide Precursor (A-1)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 58.9 g of 1-heptanol, and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0153] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0154] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The resulting crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-1). The molecular weight of polyimide precursor (A-1) was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight-average molecular weight (Mw) was found to be 26,000. The structural unit of polyimide precursor (A-1) is shown below. In the formula, n represents an integer between 5 and 200. The ratio A of polyimide precursor (A-1) was calculated from the amount charged to obtain 0.50. [ka]

[0155] <Synthesis Example 2: Synthesis of Polyimide Precursor (A-2)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 99.0 g of 2-hydroxyethyl methacrylate (HEMA), 29.4 g of 1-heptanol, and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0156] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0157] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-2). The molecular weight of the polyimide precursor (A-2) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 26,000. The structural unit of the polyimide precursor (A-2) is shown below, where n represents an integer of 5 to 200.

[0158] The ratio A of the polyimide precursor (A-2) was calculated from the charged amount and was found to be 0.75. [ka]

[0159] <Synthesis Example 3: Synthesis of Polyimide Precursor (A-3)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 33.0 g of 2-hydroxyethyl methacrylate (HEMA), 88.3 g of 1-heptanol, and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0160] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0161] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to produce a crude polymer solution. The crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The precipitate was filtered off and then vacuum dried to produce polyimide precursor (A-3).

[0162] The molecular weight of the polyimide precursor (A-3) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 27,000. The structural unit of the polyimide precursor (A-3) is shown below, where n represents an integer of 5 to 200.

[0163] The ratio A of the polyimide precursor (A-3) was calculated from the charged amount and was found to be 0.30. [ka]

[0164] <Synthesis Example 4: Synthesis of Polyimide Precursor (A-4)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 16.2 g of methanol, and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0165] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0166] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-4).

[0167] The molecular weight of the polyimide precursor (A-4) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 26,000. The structural unit of the polyimide precursor (A-4) is shown below (wherein Me represents a methyl group): where n represents an integer of 5 to 200.

[0168] The ratio A of the polyimide precursor (A-4) was calculated from the charged amount and was found to be 0.50. [ka]

[0169] <Synthesis Example 5: Synthesis of Polyimide Precursor (A-5)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 94.4 g of 1-dodecanol, and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 79.8 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0170] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0171] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-5).

[0172] The molecular weight of the polyimide precursor (A-5) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 28,000. The structural unit of the polyimide precursor (A-5) is shown below. In the formula, n represents an integer of 5 to 200.

[0173] The ratio A of the polyimide precursor (A-5) was calculated from the charged amount and was found to be 0.30. [ka]

[0174] <Synthesis Example 6: Synthesis of Polyimide Precursor (A-6)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 37.6 g of butanol, and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 79.8 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0175] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0176] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-6).

[0177] The molecular weight of the polyimide precursor (A-6) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 26,000. The structural unit of the polyimide precursor (A-6) is shown below, where n represents an integer of 5 to 200.

[0178] The ratio A of the polyimide precursor (A-6) was calculated from the charged amount and was found to be 0.30. [ka]

[0179] <Synthesis Example 7: Synthesis of polyimide precursor (A-7)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, followed by 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 29.4 g of allyl alcohol, and 400 mL of γ-butyrolactone, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0180] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0181] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-7).

[0182] The molecular weight of the polyimide precursor (A-7) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 25,000. The structural unit of the polyimide precursor (A-7) is shown below, where n represents an integer of 5 to 200.

[0183] The ratio A of the polyimide precursor (A-7) was calculated from the charged amount and was found to be 0.50. [ka]

[0184] <Synthesis Example 8: Synthesis of polyimide precursor (A-8)> 147.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was placed in a 2 L separable flask, 66.0 g of 2-hydroxyethyl methacrylate (HEMA), 58.9 g of 1-heptanol, and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had subsided, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0185] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0186] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-8).

[0187] The molecular weight of the polyimide precursor (A-8) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 22,000. The structural unit of the polyimide precursor (A-8) is shown below. In the formula, n represents an integer of 5 to 200.

[0188] The ratio A of the polyimide precursor (A-8) was calculated from the charged amount and was found to be 0.50. [ka]

[0189] <Synthesis Example 9: Synthesis of Polyimide Precursor (A-9)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 132.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0190] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 95.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0191] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-1).

[0192] The molecular weight of the polyimide precursor (A-9) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 26,000. The structural unit of the polyimide precursor (A-9) is shown below. In the formula, n represents an integer of 5 to 200.

[0193] The ratio A of the polyimide precursor (A-9) was calculated from the charged amount and was found to be 1.00. [ka]

[0194] <Synthesis Example 10: Synthesis of Polyimide Precursor (A-10)> 155.0 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a 2 L separable flask, 117.7 g of 1-heptanol and 400 mL of γ-butyrolactone were added, and the mixture was stirred at room temperature. 79.8 g of pyridine was added while stirring to obtain a reaction mixture. After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and left to stand for 16 hours.

[0195] Next, under ice cooling, a solution of 206.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 200 mL of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. Subsequently, a solution of 96.0 g of 4,4'-diaminophenyl ether (ODA) dissolved in 150 mL of γ-butyrolactone was added over 60 minutes. After further stirring at room temperature for 2 hours, 30 mL of ethyl alcohol was added and stirred for 1 hour, followed by the addition of 300 mL of N-methylpyrrolidone. The precipitate that formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0196] The resulting reaction solution was added to 3 L of ethyl alcohol to produce a precipitate consisting of a crude polymer. The crude polymer was filtered off and dissolved in 1.5 L of N-methylpyrrolidone to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 20 L of water to precipitate the polymer. The resulting precipitate was filtered off and then vacuum dried to obtain polyimide precursor (A-1).

[0197] The molecular weight of the polyimide precursor (A-10) was measured by gel permeation chromatography (standard polystyrene equivalent) and found to be a weight average molecular weight (Mw) of 25,000. The structural unit of the polyimide precursor (A-10) is shown below. In the formula, n represents an integer of 5 to 200.

[0198] The proportion A of the polyimide precursor (A-10) was calculated from the charged amount and was found to be 0. [ka]

[0199] <Preparation of Photosensitive Resin Composition> The reagents shown in the following tables were mixed in the amounts (parts by mass) shown in each table and stirred using a high-speed rotary mixer to prepare a varnish-like photosensitive resin composition. [Table 1]

[0200] The abbreviations in the table are as follows: Component (A) A-1: Polyimide precursor (A-1) synthesized in Synthesis Example 1 A-2: Polyimide precursor (A-2) synthesized in Synthesis Example 1 A-3: Polyimide precursor (A-3) synthesized in Synthesis Example 1 A-4: Polyimide precursor (A-4) synthesized in Synthesis Example 1 A-5: Polyimide precursor (A-5) synthesized in Synthesis Example 1 A-6: Polyimide precursor (A-6) synthesized in Synthesis Example 1 A-7: Polyimide precursor (A-7) synthesized in Synthesis Example 1 A-8: Polyimide precursor (A-8) synthesized in Synthesis Example 1 (F) Component A-9: Polyimide precursor (A-9) synthesized in Synthesis Example 1 A-10: Polyimide precursor (A-10) synthesized in Synthesis Example 1 4G: A compound represented by the following formula ("4G" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] (B) Component NOD-N: a compound represented by the following formula (NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] DOD-N: a compound represented by the following formula (DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] (C) Component TMPT: a compound represented by the following formula ("TMPT" manufactured by Shin-Nakamura Chemical Co., Ltd.) [ka] (D) Component OXE02: Photopolymerization initiator shown in the formula below (BASF "Irgacure OXE02") [ka] (E) Component Diethanolphenylamine: manufactured by Tokyo Chemical Industry Co., Ltd. (G) Component NMP: N-methylpyrrolidone, manufactured by Kanto Chemical Co., Ltd. KJCMPA: 3-Methoxy-N,N-dimethylpropanamide, manufactured by KJ Chemical Co.

[0201] <Evaluation of limiting resolution> A 10 μm thick copper plating was laminated on the surface of a silicon wafer, and the substrate was subjected to a phobic treatment with a 1% hydrochloric acid aqueous solution for 10 seconds. Each photosensitive resin composition was then applied to the substrate using a spin coater at a rotation speed appropriate for achieving a film thickness of 15 μm after heat treatment, and the coating was heated on a hot plate at 110°C for 3 minutes to form a photosensitive resin composition layer. This is called a laminate.

[0202] The laminate was irradiated with ultraviolet light (wavelength 365 nm, intensity 40 mW / cm 2 The exposure was performed at a dose of 50 mJ / cm. 2 to 1000mJ / cm 2 The exposure pattern used a quartz glass mask that draws round holes (via holes) with openings of 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 25 μm, and 30 μm.

[0203] Next, the entire surface of the photosensitive resin composition layer on the laminate was spray-developed with cyclopentanone as a developer at a spray pressure of 0.2 MPa for an optimal time between 30 and 200 seconds, followed by rinsing with 2-methoxy-1-methylethyl acetate (PGMEA) at a spray pressure of 0.2 MPa for 30 seconds, and then heated at 200°C for 120 minutes to cure the photosensitive resin composition layer.

[0204] The diameters of the bottoms of via holes with openings of 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 25 μm, and 30 μm in the exposure pattern were observed and measured using an SEM (magnification 1000x). The smallest size that could be opened was defined as the limiting resolution. The limiting resolution was also evaluated according to the following criteria. ○: Limiting resolution is less than 18 μm △: Limiting resolution is 18 μm or more and less than 25 μm ×: Limiting resolution is 25 μm or more

[0205] <Measurement of dielectric properties (dielectric constant, dielectric loss tangent)> To measure dielectric properties, the photosensitive resin composition was coated onto a PET film using a blade to a thickness of 140 μm. The solution on the PET film was heated at 80°C for 10 minutes using a heater to form a photosensitive film having a photosensitive resin composition layer. The photosensitive resin composition layer was peeled off from the PET film, attached to a metal frame using heat-resistant tape, and cured at 180°C for 2 hours to prepare a film for measuring physical properties.

[0206] A test piece measuring 2 mm in width and 80 mm in length was cut from the film for measuring physical properties. The dielectric constant and dielectric loss tangent of the cut test piece were measured using an Agilent Technologies HP8362B measuring device by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C.

[0207] [Table 2]

[0208] In Examples 1 to 13, it was confirmed that even when components (D) to (G) were not contained, the same results as in the above Examples were obtained, although to different degrees.

Claims

1. (A) a polyimide precursor having a structural unit represented by the following formula (A-1): (B) a crosslinking agent having two ethylenically unsaturated bonds and a divalent aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent; (C) a trifunctional or higher functional crosslinking agent, and (D) a photoradical generator, A photosensitive resin composition comprising: R in formula (A-1) contained in the entire molecule of component (A) １ and R ２ When the total number of is 1, R １ and R ２ represents the group represented by formula (A-2), and A is When the number of parts by mass of the component (B) contained in the photosensitive resin composition is b, the number of parts by mass of the component (C) contained in the photosensitive resin composition is c, and B = b / (b + c), A photosensitive resin composition that satisfies the relationship 0.2≦A×B≦0.

55. 【Chemical Formula 1】 (In formula (A-1), X1 represents a tetravalent organic group, Y1 represents a divalent organic group, and R １ and R ２ each independently represents a hydrogen atom, an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2), and n represents an integer of 2 to 200. 【Chemistry 2】 (In formula (A-2), R ３ ~R ５ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and p represents an integer of 1 to 10.

2. 2. The photosensitive resin composition according to claim 1, wherein the relationship 0.8≦a / (a+b+c)≦0.9 is satisfied, where a is the number of parts by mass of the component (A) contained in the photosensitive resin composition, b is the number of parts by mass of the component (B) contained in the photosensitive resin composition, and c is the number of parts by mass of the component (C) contained in the photosensitive resin composition.

3. In formula (A-1), R １ and R ２ each independently represents an allyl group, a monovalent aliphatic hydrocarbon group which may contain a heteroatom, or a group represented by the following formula (A-2):

4. In formula (A-1), R １ and R ２ 2. The photosensitive resin composition according to claim 1, wherein the monovalent aliphatic hydrocarbon group, which may contain a hetero atom, represented by the formula: has 1 or more and 20 or less carbon atoms.

5. 2. The photosensitive resin composition according to claim 1, wherein the content of the component (A) is 60% by mass or more and 90% by mass or less, when the total nonvolatile components of the photosensitive resin composition is 100% by mass.

6. 2. The photosensitive resin composition according to claim 1, wherein the content of the component (B) is 1% by mass or more and 25% by mass or less, when the total nonvolatile components of the photosensitive resin composition is 100% by mass.

7. 2. The photosensitive resin composition according to claim 1, wherein the content of the component (C) is 0.5% by mass or more and 10% by mass or less, when the total nonvolatile components of the photosensitive resin composition is 100% by mass.

8. The photosensitive resin composition according to claim 1 , further comprising (D) a photopolymerization initiator.

9. 2. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is thermally cured at 180° C. for 2 hours to produce a cured product having a dielectric loss tangent of 0.02 or less.

10. A photosensitive film comprising a support and a photosensitive resin composition layer formed on the support, the photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 9.

11. 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 9.

12. A semiconductor device comprising the semiconductor package substrate according to claim 11.

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