CN113448167A

CN113448167A - Photosensitive resin composition

Info

Publication number: CN113448167A
Application number: CN202110317729.1A
Authority: CN
Inventors: 霞健一
Original assignee: Ajinomoto Co Inc
Current assignee: Ajinomoto Co Inc
Priority date: 2020-03-27
Filing date: 2021-03-25
Publication date: 2021-09-28
Also published as: TW202204459A

Abstract

The invention provides a photosensitive resin composition and the like with excellent stability to a developing solution even if the developing time is prolonged. The photosensitive resin composition comprises (A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule, (B) a compound having at least 2 alkoxymethyl groups in the molecule, and (C) a photoacid generator, wherein the component (A) comprises an alkali-soluble resin having a phenolic hydroxyl group in the molecule, represented by the following formulae (A-1), (A-2), and (A-3). [ formula 1]

Description

Photosensitive resin composition

Technical Field

The present invention relates to a photosensitive resin composition. Further relates to a photosensitive film with a support obtained by using the photosensitive resin composition, a printed wiring board, a semiconductor device and a method for manufacturing the printed wiring board.

Background

Printed wiring boards widely used in various electronic devices are required to be thinned and fine wiring of circuits for miniaturization and high functionality of the electronic devices.

As a manufacturing technique of a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately laminated is known. In the manufacturing method using the build-up method, generally, a thermosetting resin composition is used for the insulating layer, and a photosensitive resin composition is used for the solder resist layer.

In recent years, it has been desired to use a photosensitive resin composition also in forming an interlayer insulating layer, and for example, patent documents 1 to 3 disclose techniques for forming an insulating layer or a solder resist using a photosensitive resin composition.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2002-

Patent document 2: japanese patent laid-open publication No. 2018-028690

Patent document 3: japanese patent laid-open publication No. 2019-060960.

Disclosure of Invention

Problems to be solved by the invention

When the insulating layer is formed using a photosensitive resin composition, the photosensitive resin composition is usually applied onto a circuit board, and is subjected to exposure and development treatment to form a pattern, thereby forming a plurality of via holes. As a result of intensive studies by the present inventors, if the thickness of the photosensitive resin composition layer after coating varies, a via hole may not be formed in a thick portion. Therefore, if the development time is prolonged so that the via hole is also formed in a thick portion, it is found that the bottom and side surfaces of the via hole are eroded by the developer in a thin portion, and the diameters of the bottoms of the plurality of via holes become uneven. Therefore, it is required to provide a photosensitive resin composition which is inhibited from being eroded by a developer even if the developing time is prolonged, that is, a photosensitive resin composition which is excellent in stability (developing time dependency) with respect to the developer.

The invention provides a photosensitive resin composition with excellent development time dependence; a photosensitive film with a support obtained by using the photosensitive resin composition, a printed wiring board, a semiconductor device, and a method for manufacturing the printed wiring board.

Means for solving the problems

As a result of intensive studies, the present inventors have found that by containing a specific component as a resin contained in a photosensitive resin composition, the stability to a developer is excellent even if the developing time is prolonged, and have completed the present invention.

That is, the present invention includes the following.

[1] A photosensitive resin composition comprising:

(A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule,

(B) A compound having at least 2 or more alkoxymethyl groups in the molecule, and

(C) a photo-acid generating agent,

(A) comprises the following components: a compound containing a structure represented by the following formula (A-1), a compound containing a structure represented by the formula (A-2), and a compound having a structure represented by the formula (A-3).

[ solution 1]

In the formula (A-1), R¹Each independently represents a 2-valent group represented by the following formula (a), X¹Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent; n1 represents an integer of 0 to 4, and m1 represents an integer of 1 to 200; denotes a bonding site;

in the formula (A-2), R²Each independently represents a 2-valent group represented by the following formula (b), a 2-valent group represented by the following formula (c), a 2-valent group formed from a combination of the 2-valent group represented by the following formula (b) and the 2-valent group represented by the following formula (c), a 2-valent group formed from a combination of the 2-valent group represented by the following formula (a) and the 2-valent group represented by the following formula (b), or a 2-valent group formed from a combination of the 2-valent group represented by the following formula (a) and the 2-valent group represented by the following formula (c), X²Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent; n2 represents an integer of 0 to 4, and m2 represents an integer of 1 to 200; denotes a bonding site;

in the formula (A-3), R³Is shown belowA 2-valent group represented by the formula (a), a 2-valent group represented by the formula (b), a 2-valent group represented by the formula (c), or a 2-valent group formed by a combination thereof, X³And X⁴Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent; n3 and n4 each independently represent an integer of 0 to 4;

[ solution 2]

In the formula (a), R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a 1-valent heterocyclic group optionally having a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R¹¹And R¹²May be bonded to each other to form a ring; denotes a bonding site;

in the formula (b), X¹¹Each independently represents an alkyl group optionally having a substituent; p1 represents an integer of 0 to 4; denotes a bonding site;

in the formula (c), X¹²And X¹³Each independently represents an alkyl group optionally having a substituent; p2 and p3 each independently represent an integer of 0 to 4; denotes a bonding site.

[2] The photosensitive resin composition according to [1], wherein the content of the compound having a structure represented by the formula (A-1) is 5% by mass or more and 85% by mass or less based on 100 parts by mass of the entire component (A).

[3] The photosensitive resin composition according to [1] or [2], wherein the content of the compound having a structure represented by the formula (A-2) is 6% by mass or more and 80% by mass or less based on 100 parts by mass of the entire component (A).

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the compound having a structure represented by formula (A-3) is 6 to 80 mass% based on 100 parts by mass of the entire component (A).

[5] The photosensitive resin composition according to any one of [1] to [4], further comprising any one of (D) an organic filler and (E) an inorganic filler.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the component (B) contains an amino resin containing at least 2 alkoxymethyl groups in a molecule.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (B) contains a melamine resin.

[8] A photosensitive film with a support, comprising: and a photosensitive resin composition layer provided on the support and containing the photosensitive resin composition described in any one of [1] to [7 ].

[9] A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of [1] to [7 ].

[10] The printed wiring board according to [9], wherein the insulating layer is a solder resist.

[11] A semiconductor device comprising the printed wiring board according to [9] or [10 ].

[12] A method for manufacturing a printed wiring board, comprising:

a step of forming a photosensitive resin composition layer containing the photosensitive resin composition according to any one of [1] to [7] on a circuit board,

A step of irradiating the photosensitive resin composition layer with active light to cure the layer,

And a step of developing the cured photosensitive resin composition layer.

Effects of the invention

According to the present invention, a photosensitive resin composition having excellent development time dependency; a photosensitive film with a support obtained by using the photosensitive resin composition, a printed wiring board, a semiconductor device and a method for manufacturing the printed wiring board.

Detailed Description

The photosensitive resin composition, the photosensitive film with a support, the printed wiring board, and the semiconductor device of the present invention will be described in detail below.

[ photosensitive resin composition ]

The photosensitive resin composition of the present invention is a photosensitive resin composition containing (a) an alkali-soluble resin having a phenolic hydroxyl group in a molecule, (B) a compound having at least 2 alkoxymethyl groups in a molecule, and (C) a photoacid generator, the component (a) containing: a compound containing a structure represented by the following formula (A-1), a compound containing a structure represented by the formula (A-2), and a compound having a structure represented by the formula (A-3).

[ solution 3]

in the formula (A-3), R³Represents a 2-valent group represented by the following formula (a), a 2-valent group represented by the following formula (b), a 2-valent group represented by the following formula (c), or a 2-valent group formed by a combination thereof, X³And X⁴Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent; n3 and n4 each independently represent an integer of 0 to 4;

[ solution 4]

By incorporating the components (a) to (C) in the photosensitive resin composition, the composition is excellent in stability to a developer and can stabilize developability even if the development time is prolonged. In the present invention, the crack resistance and the insulation property of the cured product of the photosensitive resin composition can be generally improved.

The photosensitive resin composition may further contain optional components in combination with the components (a) to (C). Examples of the optional components include (D) an organic filler, (E) an inorganic filler, (F) a solvent, and (G) other additives. Hereinafter, each component contained in the photosensitive resin composition will be described in detail.

< (A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule

The photosensitive resin composition contains an alkali-soluble resin having a phenolic hydroxyl group in the molecule as the component (a). (A) Comprises the following components: a compound containing a structure represented by the following formula (A-1), a compound containing a structure represented by the formula (A-2), and a compound having a structure represented by the formula (A-3).

[ solution 5]

[ solution 6]

A compound comprising a structure represented by the formula (A-1) -

The component (A) contained in the photosensitive resin composition contains, as the component (A-1), a compound having a structure represented by the following formula (A-1). The component (A-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ solution 7]

In the formula (A-1), R¹Each independently represents a 2-valent group represented by the following formula (a), X¹Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent. n1 represents an integer of 0 to 4, and m1 represents an integer of 1 to 200. Denotes a bonding site.

[ solution 8]

In the formula (a), R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a 1-valent heterocyclic group optionally having a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R¹¹And R¹²May be bonded to each other to form a ring. Denotes a bonding site.

X¹Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocycle optionally having a substituentAnd (4) a base. Among them, X is X from the viewpoint of remarkably obtaining the effect of the present invention¹Preferred are an alkyl group optionally having a substituent, an aryl group optionally having a substituent, and a halogen atom, more preferred is an alkyl group optionally having a substituent, an aryl group optionally having a substituent, and further preferred is an alkyl group optionally having a substituent.

The alkyl group may be a linear, branched or cyclic alkyl group, and the cyclic alkyl group may be either monocyclic or polycyclic. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, a 2-methylpropyl group, and a 3-heptyl group. Among them, a methyl group is particularly preferable from the viewpoint of remarkably obtaining the effect of the present invention.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 20 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and a fluorine atom is preferable.

The 1-valent heterocyclic group is preferably a 1-valent heterocyclic group having 3 to 21 carbon atoms, more preferably a 1-valent heterocyclic group having 3 to 15 carbon atoms, and still more preferably a 1-valent heterocyclic group having 3 to 9 carbon atoms. Among the 1-valent heterocyclic groups, 1-valent aromatic heterocyclic groups (heteroaryl groups) are also included. Examples of the 1-valent heterocyclic group include thienyl, pyrrolyl, furyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolidinyl, piperidyl, quinolyl and isoquinolyl groups. Among them, a pyrrolidinyl group is preferable. The 1-valent heterocyclic group is a group obtained by removing 1 hydrogen atom from a heterocycle of a heterocyclic compound.

R¹Each independently represents a 2-valent group represented by the formula (a). The bonding site in the formula (a) is preferably bonded to the OH group at the phenol site in the formula (A-1) at any one of ortho-, meta-and para-positions, more preferably at any one of meta-and para-positions, andone of the steps is preferably present in a mixture of meta-and para-bonded materials. When the bonding site in the formula (a) is present in a mixture of meta-and para-bonded materials with respect to the OH group of the phenol site in the formula (a-1), the bonding site in the formula (a) bonded in the meta-position is denoted by m, and the bonding site in the formula (a) bonded in the para-position is denoted by p, the mixing ratio (m: p) is preferably 1: 0.1 to 10, more preferably 1: 0.1 to 5, and more preferably 1: 0.1 to 1, particularly preferably 1: 0.5 to 2.

In the formula (a), R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a 1-valent heterocyclic group optionally having a substituent, an amino group, a carbonyl group, a carboxyl group, or a group formed by a combination thereof, R¹¹And R¹²May be bonded to each other to form a ring. Among them, a hydrogen atom and an alkyl group are preferable from the viewpoint of remarkably obtaining the effect of the present invention.

As R¹¹And R¹²Alkyl, aryl, and 1-valent heterocyclic group represented by the formula (A-1), with X in the formula (A-1)¹The alkyl, aryl, and 1-valent heterocyclic group are the same.

Examples of the group formed by a combination of these include a group formed by a combination of an alkyl group and a carbonyl group; a group formed from a combination of an aryl group and a carbonyl group; a group formed from a combination of an alkyl group, an amino group, and a carbonyl group; groups formed from combinations of aryl, amino and carbonyl groups, and the like.

R¹¹And R¹²Can be bonded to each other to form a ring, and the ring structure also includes spiro ring and condensed ring. In this case, R¹¹And R¹²Preferred are a cyclopentane ring-forming group, a cyclohexane ring-forming group, a2, 2-dimethyl-4-methylcyclohexane ring-forming group, a fluorene ring-forming group, a pyrrolidine ring-forming group, a γ -lactam ring, and the like.

Specific examples of the 2-valent group represented by the formula (a) include the following groups. In the formula, "", indicates a bonding site.

[ solution 9]

[ solution 10]

X¹Alkyl group represented by the formula, and R¹¹And R¹²The alkyl group and the aryl group represented by the formula optionally have a substituent. In the present invention, examples of the substituent in the case where each group has a substituent include a halogen atom, -OH, -O-C_1-6Alkyl, -N (C)_1-6Alkyl radical)₂、C_1-6Alkyl radical, C_6-10Aryl, -NH₂、-NH(C_1-6Alkyl), -CN, -C (O) O-C_1-6Alkyl, -C (O) H, -NO₂And the like.

In the present specification, the expression "optionally having a substituent" means, unless otherwise specified, that the substituent is unsubstituted or has 1 to 5 (preferably 1,2 or 3) substituents. When a plurality of substituents are present, the substituents may be the same or different from each other. In addition, in the present specification, "C" or "C" is used_p~C_qThe term "(p and q are positive integers, and p < q) means that the number of carbon atoms of the organic group described immediately after the term is p to q. For example, "C₁~C₆The expression "alkyl" denotes an alkyl group having 1 to 6 carbon atoms.

n1 represents an integer of 0 to 4, preferably an integer of 0 to 3, more preferably 0 or 1, and particularly preferably 1.

m1 represents an integer of 1 to 200, preferably an integer of 1 to 150, more preferably an integer of 1 to 100, and further preferably an integer of 1 to 50.

Specific examples of the component (A-1) include the following resins. In a specific example, the hydroxyl group is present in a mixture of 60% in the meta position and 40% in the para position with respect to the OH group in the phenol portion. In the following formula (1), n represents an integer of 1 to 200.

[ solution 11]

The component (A-1) may be a commercially available component, or 2 or more thereof may be used in combination. Specific examples of the commercially available component (A-1) that can be used include "TR 4020G" (a resin represented by formula (1) manufactured by Asahi organic materials Co., Ltd.); AV ライト series such as "TR 4050G", "TR 4080G", "TR 5020G", "TR 5050G", "TR 6020G", "TR 6050G" and "TR 6080G" manufactured by Asahi organic materials Co., Ltd; resin series for photoresist manufactured by sumitomo ベークライト corporation; レヂトップ series manufactured by Rong chemical industries, Inc.; フェノライト series such as "PR-30-40P", "PR-100L", "PR-100H", "PR-50", "PR-55", "PR-56-1", "PR-56-2", "WR-101", "WR-102", "WR-103", "WR-104", etc. manufactured by DIC; リグナイト, "LF-100", "LF-110", "LF-120", "LF-200", "LF-400", "LF-500"; a base resin series for photoresist manufactured by Minghe chemical company, and the like.

The component (A-1) can be usually obtained by polycondensation of phenol or a derivative thereof with an aldehyde and/or a ketone. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. Therefore, the component (A-1) is preferably terminated with an optionally substituted hydroxyphenyl group or aldehyde group, and both of the termini are preferably terminated with an optionally substituted hydroxyphenyl group.

The weight average molecular weight of the component (a-1) is preferably 500 or more, more preferably 700 or more, further preferably 1000 or more, preferably 150000 or less, more preferably 100000 or less, and further preferably 50000 or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.

The content of the component (a-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, preferably 85% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, based on 100% by mass of the entire component (a), from the viewpoint of remarkably obtaining the effects of the present invention.

In addition, the content of the component (a-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

In addition, the content of the component (a-1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, further preferably 50% by mass or less, based on 100% by mass of the resin component, from the viewpoint of remarkably obtaining the effects of the present invention. Here, the resin component means a component other than the (D) component and the (E) component.

A compound comprising a structure represented by the formula (A-2) -

The component (A) contained in the photosensitive resin composition contains, as the component (A-2), a compound having a structure represented by the following formula (A-2). The component (A-2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ solution 12]

[ solution 13]

R²Each independently represents a 2-valent group represented by the following formula (b), a 2-valent group represented by the following formula (c), a 2-valent group formed from a combination of the 2-valent group represented by the following formula (b) and the 2-valent group represented by the following formula (c), a 2-valent group formed from a combination of the 2-valent group represented by the following formula (a) and the 2-valent group represented by the following formula (b), or a 2-valent group formed from a combination of the 2-valent group represented by the following formula (a) and the 2-valent group represented by the following formula (c). For the 2-valent group represented by formula (a), as described above. The bonding sites in the formulae (a) to (c) are preferably bonded to the OH group in the phenol site in the formula (a-2) in any of the ortho, meta, and para positions, more preferably bonded to any of the meta and para positions, and further preferably bonded to both the meta and para positions. The mixing ratio of the bonding sites in the formulae (a) to (c) to the OH groups in the phenol sites in the formula (A-2) in the case where the meta-and para-bonding materials are present in a mixture is the same as that in the case of the group represented by the formula (a).

X in the formulae (b) to (c)¹¹、X¹²And X¹³Each independently represents an alkyl group optionally having a substituent. X¹¹~X¹³And X in the formula (A-1)¹The same is true.

P1, p2 and p3 in the formulae (b) to (c) each independently represents an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.

Specific examples of the 2-valent group represented by the formula (b) include the following groups. In the formula, "", indicates a bonding site.

[ solution 14]

Specific examples of the 2-valent group represented by the formula (c) include the following groups. In the formula, "", indicates a bonding site.

[ solution 15]

Specific examples of the 2-valent group formed from a combination of the 2-valent group represented by formula (b) and the 2-valent group represented by formula (c), the 2-valent group formed from a combination of the 2-valent group represented by formula (a) and the 2-valent group represented by formula (b), and the 2-valent group formed from a combination of the 2-valent group represented by formula (a) and the 2-valent group represented by formula (c) include the following groups. In the formula, "", indicates a bonding site.

[ solution 16]

X²Each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted 1-valent heterocyclic group, with X in the formula (A-1)¹The same is true.

n2 represents an integer of 0 to 4, and is the same as n1 in the formula (A-1). M2 represents an integer of 1 to 200, and is the same as m1 in the formula (A-1).

Specific examples of the component (A-2) include the following groups. In a specific example, the hydroxyl group is present in a mixture of 60% in the meta position and 40% in the para position with respect to the OH group in the phenol portion. In the following formulas (2) and (3), n represents an integer of 1 to 200.

[ solution 17]

The component (A-2) may be a commercially available component, or 2 or more thereof may be used in combination. Specific examples of commercially available components (A-2) that can be used include "MEHC-7851 SS" (resin represented by formula (2) ") and" MEHC-78004S "(resin represented by formula (3)") manufactured by Minam and Chemicals, and "MEHC-7851-SS", "MEHC-7851-S", "MEHC-7851-M", "MEHC-7851-H", "MEHC-7800-4S", "MEHC-7800-SS", "MEHC-7800-S", "MEHC-7800-M", "MEHC-7800-H", and "GPH-65", "GPH-103" and "MEHC-7841-4S" manufactured by Nippon Chemicals.

The component (A-2) can be usually obtained by polycondensation of phenol or a derivative thereof with a compound other than phenol. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. Therefore, the terminal of the component (A-2) is preferably a hydroxyphenyl group optionally having a substituent, and more preferably both terminals thereof are hydroxyphenyl groups optionally having a substituent.

The weight average molecular weight of the component (a-2) is preferably 100 or more, more preferably 300 or more, and still more preferably 500 or more, and preferably 50000 or less, more preferably 10000 or less, and still more preferably 5000 or less, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the component (a-2) is preferably 6% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, based on 100% by mass of the entire component (a), from the viewpoint of remarkably obtaining the effects of the present invention.

In addition, the content of the component (a-2) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

In addition, the content of the component (a-2) is preferably 1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less, based on 100% by mass of the resin component, from the viewpoint of remarkably obtaining the effects of the present invention.

A compound having a structure represented by the formula (A-3) -

The component (A) contained in the photosensitive resin composition contains a compound having a structure represented by the following formula (A-3) as the component (A-3). The component (A-3) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

[ solution 18]

[ solution 19]

in the formula (b), X¹¹Each independently represents an alkyl group optionally having a substituent; p1 represents an integer of 0 to 4; denotes a bondClosing;

R³Represents a 2-valent group represented by formula (a), a 2-valent group represented by formula (b), a 2-valent group represented by formula (c), or a 2-valent group formed by a combination thereof. The 2-valent groups represented by the formulas (a) - (c) are as described above.

The bonding sites in the formulae (a) to (c) are preferably bonded to the OH group in the phenol site in the formula (a-3) in any of the ortho, meta, and para positions, more preferably in any of the meta and para positions, and even more preferably in the para position.

X³And X⁴Each independently represents an optionally substituted alkyl group, an optionally substituted aryl group, a halogen atom, or an optionally substituted 1-valent heterocyclic group, with X in the formula (A-1)¹The same is true.

n3 and n4 each independently represent an integer of 0 to 4, and are the same as n1 in the formula (A-1).

Specific examples of the component (A-3) include the following groups.

[ CHEM 20 ]

[ CHEM 21 ]

[ CHEM 22 ]

[ CHEM 23 ]

[ CHEM 24 ]

[ CHEM 25 ]

[ CHEM 26 ]

[ CHEM 27 ]

[ CHEM 28 ]

[ CHEM 29 ]

The component (A-3) may be a commercially available component, or 2 or more thereof may be used in combination. Specific examples of commercially available (A-3) components that can be used include "BisE", "BisP-TMC" manufactured by chemical Co., Ltd.; "BisA", "BisF", "BisP-M" manufactured by Mitsui Chemicals ファイン; "BisP-AP", "BisP-MIBK", "BisP-B", "Bis-Z", "BisP-CP", "o, o' -BPF", "BisP-IOTD", "BisP-IBTD", "BisP-DED", "BisP-BA" manufactured by this State chemical company; "Bis-C", "Bis 26X-A", "BisOPP-A", "BisOTBP-A", "BisOCHP-A", "BisOFP-A", "BisOC-Z", "BisOC-FL", "BisOC-CP", "BisOCHP-Z", "メチレンビス P-CR", "TM-BPF", "BisOC-F", "Bis 3M 6B-IBTD", "BisOC-IST", "BisP-PRM", "BisP-LV", and the like, manufactured by chemical company of this state.

The molecular weight of the component (a-3) is preferably 150 or more, more preferably 160 or more, and still more preferably 170 or more, and preferably 1000 or less, more preferably 800 or less, and still more preferably 500 or less, from the viewpoint of remarkably obtaining the effect of the present invention.

The content of the component (a-3) is preferably 6% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, based on 100% by mass of the entire component (a), from the viewpoint of remarkably obtaining the effects of the present invention.

In addition, the content of the component (a-3) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

In addition, the content of the component (a-3) is preferably 1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 50% by mass or less, based on 100% by mass of the resin component, from the viewpoint of remarkably obtaining the effects of the present invention.

When the content of the component (A-1) is denoted as a1 when the whole component (A) is 100 mass% and the content of the component (A-2) is denoted as a2 when the whole component (A) is 100 mass%, a2/a1 is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 1 or less, from the viewpoint of remarkably obtaining the effects of the present invention.

When the content of the component (a-3) is expressed as a3, a3/a1 is preferably 0.01 or more, more preferably 0.05 or more, more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and further preferably 1 or less, from the viewpoint of remarkably obtaining the effect of the present invention, when the total of the component (a) is 100 mass%.

In addition, the a2/a3 is preferably 0.2 or more, more preferably 0.25 or more, more preferably 0.3 or more, preferably 5 or less, more preferably 3 or less, and even more preferably 1.5 or less, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the component (a) is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the component (a) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less, based on 100% by mass of the resin component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

< (B) A compound having at least 2 alkoxymethyl groups in the molecule

The photosensitive resin composition contains, as the component (B), a compound (B) containing at least 2 alkoxymethyl groups in the molecule. (B) The component (A) has a function of reacting with the component (A) to form a crosslinked structure. (B) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The alkoxymethyl group is a group represented by the following formula (B-1). In the formula, "", indicates a bonding site.

[ solution 30]

In the formula (B-1), R²¹Represents an alkyl group optionally having a substituent.

R²¹Represents an optionally substitutedAn alkyl group. The alkyl group may be a linear, branched or cyclic alkyl group, and the cyclic alkyl group may be either monocyclic or polycyclic. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, a sec-butyl group, and a tert-butyl group. Among them, methyl and butyl are preferable, and methyl is more preferable, from the viewpoint of remarkably obtaining the effect of the present invention.

R²¹The alkyl group represented may have a substituent.

The alkoxymethyl group is preferably an alkoxymethylamino group represented by the following formula (B-1'). In the formula, "", indicates a bonding site.

[ solution 31]

In the formula (B-1'), R²²And R in the formula (B-1)²¹The same is true. R represents a hydrogen atom or an alkoxymethyl group.

As the component (B), a compound containing at least 2 or more alkoxymethyl groups in the molecule can be used, and examples of such a compound include an amino resin containing at least 2 or more alkoxymethyl groups in the molecule, a phenol resin containing at least 2 or more alkoxymethyl groups in the molecule, and the like. Among them, from the viewpoint of obtaining a photosensitive resin composition having more excellent photosensitivity, an amino resin containing at least 2 or more alkoxymethyl groups in the molecule is preferable.

Examples of the amino resin having at least 2 or more alkoxymethyl groups in the molecule include melamine resin and urea resin, with melamine resin being preferred.

The melamine resin is preferably a melamine resin having a structural unit represented by the following formula (B-2), for example.

[ solution 32]

In the formula (B-2), X²¹、X²²、X²³And X²⁴、X²⁵And X²⁶Each independently represents a hydrogen atom or an alkoxymethyl group. R⁵⁰Represents a hydrogen atom, an amino group, an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkoxymethylamino group represented by the formula (B-1'). However, at R⁵⁰X represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group²¹、X²²、X²³And X²⁴At least 2 of which are alkoxymethyl groups.

X²¹~X²⁴The alkoxymethyl group is the same as that of the formula (B-1). At R⁵⁰X represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group²¹~X²⁴At least 2 of (a) are alkoxymethyl groups, preferably X²¹~X²⁴At least 3 of (a) are alkoxymethyl groups, more preferably X²¹~X²⁴At least 4 of which are alkoxymethyl groups.

R⁵⁰Represents a hydrogen atom, an amino group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxymethylamino group represented by the formula (B-1'), preferably an aryl group which may have a substituent, an alkoxymethylamino group represented by the formula (B-1'), more preferably an alkoxymethylamino group represented by the formula (B-1 '). An alkyl group optionally having a substituent and R in the formula (a)¹¹The alkyl group is the same as the alkyl group, and the aryl group optionally having a substituent is the same as R in the formula (a)¹¹The aryl groups represented are the same.

The melamine resin having the structural unit represented by the formula (B-2) is preferably a melamine resin having the structural unit represented by the formula (B-2').

[ solution 33]

In the formula (B-2'), X²⁵、X²⁶、X²⁷、X²⁸、X²⁹And X³⁰Each independently represents a hydrogen atom or an alkoxymethyl group. However, X²⁵、X²⁶、X²⁷、X²⁸、X²⁹And X³⁰At least 2 of which are alkoxymethyl groups.

X²⁵~X³⁰The alkoxymethyl group is the same as that of the formula (B-1). X²⁵~X³⁰At least 2 of (a) are alkoxymethyl groups, preferably X²⁵~X³⁰At least 3 of (a) are alkoxymethyl groups, more preferably X²⁵~X³⁰At least 4 of them are alkoxymethyl groups, further preferably X²⁵~X³⁰All are alkoxymethyl groups.

Specific examples of the melamine resin include the following melamine resins.

[ chemical 34]

The melamine resin may be a commercially available one. Examples of commercially available products include "MW-390", "MW-100 LM", "MX-750 LM" manufactured by Sanyo ケミカル Co; オルネクスジャパン, サイメル series.

Melamine resins can be prepared, for example, by polycondensation of melamine with formaldehyde.

As the urea resin, for example, a urea resin having either a structural unit represented by the following formula (B-3) or a structural unit represented by the following formula (B-4) is preferable.

[ solution 35]

In the formula (B-3), X³¹、X³²、X³³And X³⁴Each independently represents a hydrogen atom or an alkoxymethyl group. However, X³¹、X³²、X³³And X³⁴At least 2 of which are alkoxymethyl groups.

In the formula (B-4), X³⁵And X³⁶Represents an alkoxymethyl group.

X³¹~X³⁸The alkoxymethyl group is the same as that of the formula (B-1). X³¹~X³⁴At least 2 of (a) are alkoxymethyl groups, preferably X³¹~X³⁴At least 3 of (a) are alkoxymethyl groups, more preferably X³¹~X³⁴At least 4 of which are alkoxymethyl groups.

The urea resin may be a commercially available one. Examples of commercially available products include "MX-270", "MX-279" and "MX-280" manufactured by Sanhe ケミカル Co; オルネクスジャパン, サイメル series.

Urea resins can be prepared, for example, by polycondensation of urea with formaldehyde.

The phenol resin containing at least 2 alkoxymethyl groups in the molecule is preferably a phenol resin having a structural unit represented by the following formula (B-5), for example.

[ solution 36]

In the formula (B-5), X³⁹Represents an alkoxymethyl group, R²³And R²⁴Each independently represents an alkyl group optionally having a substituent, R²⁵Represents a single bond or a 2-valent organic group. s and t each independently represent an integer of 1 to 3, and u and v each independently represent an integer of 0 to 4.

X³⁹The alkoxymethyl group is the same as that of the formula (B-1). R²³And R²⁴An optionally substituted alkyl group represented by the formula (A-1) with X¹The alkyl groups optionally having a substituent are the same.

R²⁵Represents a single bond or a 2-valent organic group. Examples of the 2-valent organic group include an alkylidene group having 2 to 10 carbon atoms such as an alkylene group having 1 to 10 carbon atoms and an ethylidene group such as a methylene group, an ethylene group, and a propylene group, and a phenylene group6 to 30 arylene groups, groups obtained by substituting a part or all of the hydrogen atoms of these hydrocarbon groups with a halogen atom such as a fluorine atom, sulfonyl groups, carbonyl groups, ether linkages, thioether linkages, amide linkages, and the like.

The content of the component (B) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, based on 100 mass% of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

The content of the component (B) is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, based on 100 mass% of the resin component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effect of the present invention.

(C) photoacid generators

The photosensitive resin composition contains a photoacid generator as component (C). (C) The photoacid generator can generate an acid upon irradiation with active light such as ultraviolet light, and the reaction of the component (a) and the component (B) is promoted by the generated acid to favorably form a negative pattern. (C) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the photoacid generator, a compound that generates an acid by irradiation of active light can be used. Examples of such a photoacid generator include halogen-containing compounds, onium salt compounds, diazoketone compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, diazomethane compounds, oxime ester compounds, and the like. Among them, a halogen-containing compound is preferable from the viewpoint of remarkably obtaining the effect of the present invention.

Examples of the halogen-containing compound that can be suitably used as the photoacid generator include a hydrocarbon compound containing a halogenated alkyl group, a heterocyclic compound containing a halogenated alkyl group, and the like. Suitable examples of the halogen-containing compound include 2- [2- (furan-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- (methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-methoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (3, 4-dimethoxyphenyl) vinyl ] -4, 6-bis (trichloromethyl) -s-triazine, 1, 10-dibromo-n-decane, n-trifluoromethyl-tert-decane, n-butyl-trifluoromethyl-tert-triazine, n-butyl-trifluoromethyl-triazine, n-butyl-methyl-2- (trifluoromethyl) vinyl ] -4, 6-trifluoromethyl-s-triazine, n-butyl-methyl-triazine, n-butyl-methyl-ethyl-methyl-triazine, ethyl-butyl-ethyl-butyl-ethyl, And s-triazine derivatives such as 1, 1-bis (4-chlorophenyl) -2,2, 2-trichloroethane, phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, and naphthyl-bis (trichloromethyl) -s-triazine.

As the halogen-containing compound, commercially available products may be used, and examples thereof include "TFE-triazine", "TME-triazine", "MP-triazine", "MOP-triazine" and "dimethoxytriazine" (a halogen-containing compound photoacid generator having a triazine skeleton) manufactured by Sanzha ケミカル Co.

Examples of the onium salt compound that can be suitably used as a photoacid generator include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Suitable specific examples of the onium salt compound include tris (4-methylphenyl) sulfonium trifluoromethanesulfonate, tris (4-methylphenyl) sulfonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyl diphenylsulfonium p-toluenesulfonate, 4, 7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate and the like.

As the onium salt compound, commercially available products can be used, and examples thereof include "TS-01" and "TS-91" manufactured by Sanhe ケミカル Co; サンアプロ, "CPI-110A", "CPI-210S", "HS-1", "LW-S1", "IK-1", "CPI-310B"; the products of the three chemical industries are SI-110L, SI-180L, SI-100L, and the like.

Examples of the diazoketone compound that can be suitably used as a photoacid generator include a1, 3-diketo-2-diazo compound, a diazoquinone compound, a diazonaphthoquinone compound, and the like. Suitable specific examples of the diazoketone compound include a1, 2-naphthoquinone diazo-4-sulfonate compound of a phenol type.

Examples of the sulfone compound that can be suitably used as the photoacid generator include β -ketosulfone compounds, β -sulfonylsulfone compounds, and α -diazo compounds of these compounds. Suitable specific examples of the sulfone compound include 4-tribenzoylmethylsulfone, mesitylbenzoylmethylsulfonylsulfone, and bis (benzoylmethylsulfonyl) methane.

Examples of the sulfonic acid compound that can be suitably used as the photoacid generator include alkyl sulfonates, halogenated alkyl sulfonates, aryl sulfonates, and imino sulfonates. Suitable specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), o-nitrobenzyl trifluoromethanesulfonate, o-nitrobenzyl-p-toluenesulfonate and the like.

Specific examples of the sulfonimide compound which can be suitably used as a photoacid generator include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like.

Specific examples of the diazomethane compound which can be suitably used as a photoacid generator include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and the like. As the diazomethane compound, a commercially available product can be used.

Specific examples of oxime ester compounds which can be suitably used as a photoacid generator include phenylacetonitrile, 2-methyl- α - [2- [ [ (propylsulfonyl) oxy ] imino ] -3(2H) -thienylidene ] (benzacetanilino, 2-methyl- α - [2- [ [ (propylsulfonyl) oxy ] imino ] -3(2H) -thienylidene ]), phenylacetonitrile, 2-methyl- α - [2- [ [ [ (4-methylphenyl) sulfonyl ] oxy ] imino ] -3(2H) -thienylidene ] (benzacetanilino, 2-methyl- α - [2- [ [ [ (4-methylphenenyl) sulfonyl ] oxy ] imino ] -3(2H) -thienylidene ]), and the like. Examples of commercially available products include Irgacure series "PAG 103", "PAG 121", "PAG 169", and "PAG 203" manufactured by BASF corporation.

(C) The content of the photoacid generator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, preferably 3% by mass or less, more preferably 1.5% by mass or less, when the nonvolatile content in the photosensitive resin composition is taken as 100% by mass.

< (D) organic filling Material

The photosensitive resin composition may further contain (D) an organic filler as an optional component. (D) The organic filler exhibits flexibility, and therefore can disperse stress of a cured product of the photosensitive resin composition, and as a result, can improve crack resistance and insulation properties.

Examples of the component (D) include fine polyurethane particles, fine rubber particles, fine polyamide particles, and fine silicone particles.

As the polyurethane fine particles, commercially available ones can be used, and examples thereof include "MM-101 SW", "MM-101 SWA", "MM-101 SM", "MM-101 SMA" and "MM-110 SMA" manufactured by Industrial Co., Ltd; レジナス into RKB series manufactured by Inc.

The rubber particles may be any particles of resin as long as they are microparticles of resin obtained by chemically crosslinking a resin exhibiting rubber elasticity so as to be insoluble and infusible in an organic solvent, and examples thereof include acrylonitrile butadiene rubber particles, acrylic rubber particles, and methyl methacrylate-butadiene-styrene copolymer particles. As the rubber particles, commercially available ones can be used, and examples thereof include "EXL-2655" manufactured by ダウ & ケミカル Japan; ガンツ "AC 3816N", "AC 3355", "AC 3816", "AC 3832", "AC 4030", "AC 3364" and "IM 101" manufactured by Kabushiki Kaisha; "パラロイド EXL 2655" and "EXL 2602" manufactured by Wuhui chemical company; カネカ, "B-11A", "B513", "B22", "B-521", "B-561", "B-564", "FM-21", "FM-40", "FM-50", "M-701", "M-711", "M-732", "M-300", "FM-40", "M-570", "M-210"; レジナス into RKB series manufactured by Inc.

As the polyamide fine particles, fine particles having a particle size of 50 μm or less of the resin having an amide bond can be used, and examples thereof include aliphatic polyamides such as nylon, aromatic polyamides such as kevlar, and polyamideimides. As the polyamide fine particles, commercially available products can be used, and examples thereof include "VESTOSINT 2070" manufactured by ダイセルヒュルス Co; "SP 500" manufactured by east レ Co.

(D) The average particle diameter of the organic filler is preferably 0.005 μm or more or 0.02 μm or more, more preferably 0.2 μm or more, preferably 1 μm or less, more preferably 0.6 μm or less. (D) The average particle size of the organic filler can be measured using a dynamic light scattering method. (D) The average particle diameter of the organic filler can be measured, for example, by uniformly dispersing the organic filler in an appropriate organic solvent by ultrasonic wave or the like, preparing a particle size distribution of the organic filler on a mass basis using a concentrated particle size analyzer (FPAR-1000; available from Otsuka Denshi Co., Ltd.), and recording the median diameter as the average particle diameter.

(D) The content of the organic filler is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, based on 100% by mass of the nonvolatile component of the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

(E) inorganic filler

The photosensitive resin composition may contain (E) an inorganic filler as an optional component. By containing (E) an inorganic filler in the resin composition, a cured product having excellent insulation properties can be obtained.

As a material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate phosphate, and the like. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Further, the silica is preferably spherical silica. (E) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of commercially available products of the inorganic filler (E) include "UFP-30" manufactured by デンカ Co; "SP 60-05" and "SP 507-05" manufactured by Xinri iron guo \12510and "12486 リアルズ; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by アドマテックス; デンカ entitled "UFP-30"; トクヤマ, "シルフィル NSS-3N", "シルフィル NSS-4N" and "シルフィル NSS-5N"; アドマテックス, "SC 2500 SQ", "SO-C4", "SO-C2", "SO-C1", and "SC 2050-SXF".

(E) The average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, preferably 5 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less, from the viewpoint of remarkably obtaining the desired effect of the present invention.

(E) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis by a laser diffraction scattering particle size distribution measuring apparatus, and the median diameter is measured as an average particle size. The measurement sample used was prepared by weighing 100mg of the inorganic filler and 10g of methyl ethyl ketone in a vial and dispersing them with ultrasound for 10 minutes. The volume-based particle size distribution of the inorganic filler was measured in a flow cell system using a laser diffraction particle size distribution measuring apparatus with the wavelengths of the light source used being blue and red, and the average particle size was calculated from the obtained particle size distribution as the median diameter. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Inc.

(E) The specific surface area of the inorganic filler is preferably 1m from the viewpoint of remarkably obtaining the desired effect of the present invention²A ratio of 2m or more, more preferably 2m²A specific ratio of 3m or more in terms of/g²More than g. The upper limit is not particularly limited, but is preferably 60m²Less than 50 m/g²Less than or equal to 40 m/g²The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area was obtained by measuring the specific surface area of the inorganic filler by adsorbing nitrogen gas on the surface of the sample using a BET full automatic specific surface area measuring apparatus (Macsorb HM-1210 manufactured by マウンテック), and calculating the specific surface area using a BET multipoint method.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilicon azane compounds, titanate coupling agents, and the like. Further, the surface treatment agent may be used alone in 1 kind, or may be used in any combination of 2 or more kinds.

Examples of commercially available surface-treating agents include "KBM 403" (3-glycidoxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM-503" (3-methacryloxypropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 803" (3-mercaptopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBE 903" (3-aminopropyltriethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM 573" (N-phenyl-3-aminopropyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "SZ-31" (hexamethyldisilazane) available from shin-Etsu chemical Co., Ltd, "KBM 103" (phenyltrimethoxysilane) available from shin-Etsu chemical Co., Ltd, "KBM-4803" (long-chain epoxy-type silane coupling agent), KBM-7103 (3,3, 3-trifluoropropyltrimethoxysilane) manufactured by shin-Etsu chemical industries, Ltd.

The degree of surface treatment with the surface treatment agent preferably falls within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of a surface treatment agent, more preferably 0.2 to 3 parts by mass, and most preferably 0.3 to 2 parts by mass.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler²Above, more preferably 0.1mg/m²Above, more preferably 0.2mg/m²The above. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet state, it is preferably 1mg/m²Less than, more preferably 0.8mg/m²The concentration is preferably 0.5mg/m or less²The following.

(E) The amount of carbon per unit surface area of the inorganic filler material can be measured after subjecting the surface-treated inorganic filler material to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, as a solvent, a sufficient amount of MEK was added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic washing was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid content, the amount of carbon per surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, Ltd.

The content of the inorganic filler (E) is preferably 1 mass% or more, more preferably 5 mass% or more, further preferably 10 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, and further preferably 60 mass% or less, based on 100 mass% of the nonvolatile component in the photosensitive resin composition, from the viewpoint of remarkably obtaining the effects of the present invention.

(E) When the total content of the inorganic filler and the organic filler (D) is represented by β when the nonvolatile content of the photosensitive resin composition is 100% by mass, and the content of the component (a) when the nonvolatile content of the photosensitive resin composition is 100% by mass is represented by α, β/α is preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.1 or more, preferably 3 or less, more preferably 2.5 or less, further preferably 2 or less, or 1 or less, from the viewpoint of remarkably obtaining the effect of the present invention.

(F) solvent

The photosensitive resin composition may further contain (F) a solvent as an optional component. By containing the (F) solvent, the varnish viscosity can be adjusted. Examples of the solvent (F) include organic solvents.

Examples of the solvent (F) include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate, and ethyl diethylene glycol acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha. These may be used alone in 1 kind, or in combination of 2 or more kinds. The content of the solvent used may be appropriately adjusted from the viewpoint of coatability of the resin composition.

< (G) other additives

The photosensitive resin composition may further contain (G) other additives to the extent that the object of the present invention is not impaired. As (G) other additives, for example, thermoplastic resins; silane coupling agents such as vinyl silane coupling agents, epoxy silane coupling agents, styrene silane coupling agents, methacryl silane coupling agents, acryl silane coupling agents, aminosilane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, isocyanate silane coupling agents, and anhydride silane coupling agents; nitrogen atom-and/or sulfur atom-containing compounds such as triazine thiols (e.g., 2,4, 6-trimercapto-s-triazine, 2-dibutylamino-4, 6-dimercapto-s-triazine, N' -tert-butyl-N-cyclopropyl-6- (methylthio) -1,3, 5-triazine-2, 4-diamine), piperidines, pyrazoles (e.g., 3, 5-dimethylpyrazole, 3-methyl-5-pyrazolone), triazoles (e.g., 1,2, 4-triazole, 3-mercapto-1, 2, 4-triazole), benzotriazoles (e.g., 1,2, 3-benzotriazole, 1-hydroxybenzotriazole), etc.; 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, pyrogallol, etc.; thickeners such as bentonite and montmorillonite; silicone, fluorine, and vinyl resin defoaming agents; flame retardants such as epoxy resins, antimony compounds, phosphorus compounds, aromatic condensed phosphoric esters, and halogen-containing condensed phosphoric esters; and various additives such as a phenol-based curing agent, a cyanate ester-based curing agent, and the like.

Examples of commercially available products of the silane coupling agent include "KBM-1003", "KBE-1003", "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403", "KBM-1403", "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103", "KBM-602", "KBM-603", "KBM-903", "KBE-9103P", "KBM-573", "KBM-575", "KBM-9659", "KBE-585A", "KBM-802", "KBM-803", "KBE-9007N" and "X-12-967C", manufactured by shin-Etsu chemical industries. Preferred examples of these commercially available products include "KBM-303", "KBM-402", "KBM-403", "KBE-402" and "KBE-403", and among these, "KBM-403" is more preferably used. The silane coupling agent as (G) other additive is preferably used separately from the surface treatment agent for (E) inorganic filler material.

Examples of commercially available products of compounds containing a nitrogen atom and/or a sulfur atom include "ジスネット f (ttca)", "ジスネット DB", and "SanAlga 1907" manufactured by sansynergists; "BSH", "IBSH", "ASH", "IPSH", "ESH" of the actar (registered trademark) series manufactured by kayokoku corporation, "VBATDT" (6- (4-vinylbenzyl-n-propyl) amino-1, 3, 5-triazine-2, 4-dithiol) manufactured by kayokoku corporation; "ノクセラー TCA", "ノクセラー H", "ノクセラー 8", "ノクセラー 8-N", "ノクセラー TMU", "ノクセラー EUR", "ノクセラー D", "ノクセラー DT", "ノクセラー PR", "ノクセラー M-P", "ノクセラー DM-P", "ノクセラー MZ", "ノクセラー M-60-OT", "ノクセラー MDB-P", "ノクセラー CZ-G", "ノクセラー MSA-G", "ノクセラー TT-P", "ノクセラー TET-G", "ノクセラー TBT.TBT-N", "ノクセラー TOT-N", "ノクセラー TS", "ノクセラー TRA "ノクセラー PZ", "ノクセラー EZ", "ノクセラー BZ-P", "ノクセラー PX", "ノクセラー ZP", "ノクセラー ZTC", "ノクセラー TP", "ノクセラー TTCU", "ノクセラー TTTE", "ノクセラー ZIX-O", "ノクセラー F", "ノクセラー MIX No. 2", "ノクセラー MIX No. 3", "ノクセラー EP-55", "ノクセラー EP-60", "ノクセラー EP-90", "ノクラック 224", "ノクラック AW", "ノクラック AW-N", "ノクラック B", "ノクラック B-N", "ノクラック PA", "ノクラック ODA"), "ノクラック ODA-N", "ノクラック AD-F", "ノクラック CD", "ノクラック TD", "ノクラック White", "ノクラック 810-NA", "ノクラック 6C", "ノクラック G-1", "ノクラック 300", "ノクラック MB", "ノクラック MMB", "ノクラック MBZ", "ノクラック NBC", "ノクラック TNP", "ノクラック 400", "スコノック", "リターダー CTP", "バルノック GM-P", "バルノック DGM", "バルノック R", "バルノック DNB", "バルノック AB-S", "バルノック PM", "ノクタイザー SS"; "BT-120", "BT-120 SG", "BT-LX", "CBT-1", "CBT-SG", "TT-LX", "TT-LYK", "JCL-400", "TT-130F", "JF-77", "JF-79", "JF-80", "JF-83", "JF-832", "JAST-500", "JF-90G" and "JF-95" manufactured by North City chemical company; 3, 5-dimethylpyrazole, 3-methyl-5-pyrazolone, 1,2, 4-triazole, 3-mercapto-1, 2, 4-triazole, and 1-hydroxybenzotriazole available from Otsuka chemical Co., Ltd; "Crystal # 120" (1, 2, 3-benzotriazole), "TTA" (tolyltriazole), "VT-120M" (5-methyl-1H-benzotriazole), "C-BTA" (carboxybenzotriazole), "N-BTA" (nitro-1H-benzotriazole), "TT-250A" (benzotriazole derivative), "OA-386" (benzotriazole derivative), "OA-372" (N, N-bis (2-ethylhexyl) (1H-benzotriazole-1-yl) methylamine), manufactured by Dahe chemical company, "NEW DAIN SILVER OIL RD". Preferred examples of these commercially available products include "BSH", "IBSH", "ASH", "IPSH", "ESH" available from Kakoku corporation of Actor (registered trademark), "VBATDT" (6- (4-vinylbenzyl-n-propyl) amino-1, 3, 5-triazine-2, 4-dithiol) available from Kakoku corporation, "ジスネット F (TTCA))" (triazine trithiol) available from Triplex corporation, "ジスネット DB" (2-butylamino-4, 6-dimercapto-s-triazine available from Danei Kagaku corporation of "ノクセラー TCA" (triazine trithiol) available from Danei Kagaku corporation of Tokyo corporation of "BT-120" (1, 2, 3-benzotriazole) and "BT-120 SG" (1, 2, 3-benzotriazole) available from Tokyo chemical corporation of Tokyo, VERZONE Crystal #120 (1, 2, 3-benzotriazole) from DAHECHE CHEMICAL CORPORATION.

The photosensitive resin composition can be produced by: the components (a) to (C) are mixed as essential components, the components (D) to (G) are appropriately mixed as optional components, and if necessary, the mixture is kneaded or stirred by a kneading means such as a three-roll mill, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or a planetary mixer.

< Properties and applications of photosensitive resin composition >

The photosensitive resin composition exhibits excellent characteristics in stability to a developer (development time dependency) even when the development time is prolonged. Evaluation of development time dependency the bottom diameter of the via hole with 20 μm of the opening of the exposure pattern was measured for the cases where the development time was 30 seconds, 60 seconds, 90 seconds, and 120 seconds. In this case, the greater the number of development times for which the bottom diameter of the via hole is 15 μm or more and 20 μm or less, the more excellent the development time dependency is evaluated. In this case, the number of development times for which the diameter of the bottom of the via is 15 μm or more and 20 μm or less is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The evaluation of development time dependence can be measured by the method described in the examples below.

A cured product obtained by photocuring a photosensitive resin composition generally exhibits excellent crack resistance. Therefore, the cured product provides an insulating layer having excellent crack resistance. The evaluation of the crack resistance was carried out by the following tests: after exposure to the atmosphere at-40 ℃ for 15 minutes, the temperature was raised at a rate of 180 ℃/minute, and then, after exposure to the atmosphere at 160 ℃ for 15 minutes, the temperature was lowered at a rate of 180 ℃/minute, and the heat cycle treatment was repeated 1000 times. In this case, cracks and separation were not observed preferably 200 times later, more preferably 500 times later. The crack resistance can be evaluated by the method described in the examples described later.

A cured product obtained by photocuring a photosensitive resin composition generally shows such a characteristic that the insulation property after a HAST test (100 hours or 200 hours in an environment at 130 ℃ and a relative humidity of 85%) is excellent. Therefore, the cured product provides an insulating layer having excellent insulating properties. For the insulation, those after 100 hours are preferableInsulation resistance value lower than 1 x 10⁷The wiring of Ω is 1 or less among 6 portions, and the insulation resistance value after 200 hours is more preferably less than 1 × 10⁷The wiring of Ω is 1 or less among 6 portions. The insulation property can be evaluated by the method described in the examples described later.

The application of the photosensitive resin composition of the present invention is not particularly limited, and the photosensitive resin composition can be used in a wide range of applications requiring a photosensitive resin composition, such as a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (for a laminate, a multilayer printed wiring board, and the like), a solder resist, an underfill material, a die attach material, a semiconductor sealing material, a via filling resin, a component embedding resin, and the like. Among them, a photosensitive resin composition for an insulating layer (a printed wiring board using a cured product of a photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a printed wiring board using a cured product of a photosensitive resin composition as an interlayer insulating layer), a photosensitive resin composition for plating formation (a printed wiring board on which a plating layer is formed on a cured product of a photosensitive resin composition), and a photosensitive resin composition for a solder resist (a printed wiring board using a cured product of a photosensitive resin composition as a solder resist), a photosensitive resin composition for a rewiring layer of a wafer level package (a wafer level package using a cured product of a photosensitive resin composition as a rewiring layer), a photosensitive resin composition for a rewiring layer of a fan-out wafer level package (a fan-out wafer level package using a cured product of a photosensitive resin composition as a rewiring layer), which can be suitably used as a printed wiring board, a method for manufacturing a semiconductor device, and a semiconductor device, The photosensitive resin composition for the rewiring layer of the fan-out panel level package (fan-out panel level package with the cured product of the photosensitive resin composition as the rewiring layer), the photosensitive resin composition for the buffer coating (semiconductor device with the cured product of the photosensitive resin composition as the buffer coating), and the photosensitive resin composition for the insulating layer of the display (display with the cured product of the photosensitive resin composition as the insulating layer).

[ photosensitive film with support ]

The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support, in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support includes: and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

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

Examples of commercially available supports include, but are not limited to, polypropylene films such as "アルファン MA-410" and "E-200C" manufactured by Wangzi paper company, and polyethylene terephthalate films such as PS-series films such as "PP-25" manufactured by Tekken company. These supports may be coated with a release agent such as a silicone coating agent on the surface for easy removal. The thickness of the support is preferably in the range of 5 to 50 μm, and more preferably in the range of 10 to 25 μm. By setting the thickness to 5 μm or more, the support can be suppressed from cracking when the support is peeled off before development, and by setting the thickness to 50 μm or less, the resolution when the support is exposed from the support can be improved. In addition, a support with low fish eye spots is preferred. Here, the fish-eye spots are obtained by incorporating foreign matters, undissolved matters, oxidation-degraded matters, and the like of a material into a film when the material is thermally melted and the film is produced by kneading, extrusion, biaxial stretching, casting, or the like.

Further, the photosensitive resin composition layer may be protected by a protective film. By protecting the photosensitive resin composition layer side of the photosensitive film with the support with the protective film, it is possible to prevent adhesion of dirt and the like on the surface of the photosensitive resin composition layer and scratches. As the protective film, a film made of the same material as the support described above can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. By setting the thickness to 1 μm or more, the handling property of the protective film can be improved, and by setting the thickness to 40 μm or less, the cost tends to be good. The protective film preferably has a smaller adhesion between the photosensitive resin composition layer and the protective film than between the photosensitive resin composition layer and the support.

The photosensitive film with a support can be produced by, for example, applying the photosensitive resin composition to a support and drying the component (F) by heating, hot air blowing, or the like, according to a method known to those skilled in the art. The photosensitive resin composition can be produced, for example, by using a resin varnish containing the nonvolatile component and an excess amount of the component (F) of the photosensitive resin composition. Specifically, first, after the bubbles in the resin varnish are completely removed by a vacuum defoaming method or the like, the resin varnish is applied to a support, and the amount of the component (F) is adjusted by drying in a hot-air furnace or a far-infrared furnace, whereby a photosensitive film with a support including a photosensitive resin composition layer formed of a photosensitive resin composition can be produced. One embodiment of a method for producing a photosensitive film with a support is obtained by drying a resin varnish with a maximum temperature of 105 ℃ to 135 ℃ and a drying time of 6 minutes to 20 minutes.

The drying temperature varies depending on the curability of the photosensitive resin composition and the amount of the component (F) in the resin varnish, and can be 50 ℃ to 120 ℃. However, the maximum temperature for drying is preferably 60 ℃ or higher, and more preferably 80 ℃ or higher, from the viewpoint of obtaining a cured product having excellent undercut resistance. The lower limit of the maximum temperature is not particularly limited, but is preferably 135 ℃ or lower, more preferably 130 ℃ or lower.

The drying time varies depending on the curability of the photosensitive resin composition and the amount of the component (F) in the resin varnish, and is preferably 6 minutes or more, preferably 30 minutes or less, and more preferably 20 minutes or less. Here, the drying time is a time from when the drying temperature reaches 60 ℃.

The residual amount of the component (F) in the photosensitive resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 2% by mass or less, based on the total amount of the photosensitive resin composition layer. The person skilled in the art can suitably set suitable drying conditions by simple experiments.

The thickness of the photosensitive resin composition layer may be set in a range of 1 μm or more and 100 μm or less according to the purpose from the viewpoint of improving handling properties and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer. The thickness of the photosensitive resin composition layer is, for example, preferably 10 μm or more, more preferably 15 μm or more, further preferably 20 μm or more, preferably 30 μm or less, more preferably 28 μm or less, further preferably 25 μm or less.

[ printed Wiring Board ]

The printed wiring board of the present invention comprises 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 solder resist.

Specifically, the printed wiring board of the present invention can be produced using the photosensitive film with a support. Specifically, the method for manufacturing a printed wiring board includes:

(I) a step of forming a photosensitive resin composition layer comprising the photosensitive resin composition of the present invention on a circuit board,

(II) curing the photosensitive resin composition layer by irradiating it with active light, and

(III) a step of developing the cured photosensitive resin composition layer.

Hereinafter, an example of a case where the insulating layer is a solder resist will be described.

< step (I) >

Examples of the method for forming the photosensitive resin composition layer include a method in which a resin varnish containing a photosensitive resin composition is directly applied to a circuit board, and a method in which the photosensitive film with a support is used.

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

Examples of the coating method of the resin varnish include a gravure coating method, a microgravure coating method, a reverse coating method, a contact reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, a roll coating method, a knife coating method, a curtain coating method, a cavity gravure coating method, a slot hole method, a spin coating method, a slot coating method, a spray coating method, a dip coating method, a hot melt coating method, a bar coating method, an applicator method, an air knife coating method, a curtain flow coating method, an offset printing method, a brush coating method, a full-surface printing method by a screen printing method, and the like.

The resin varnish may be applied in a plurality of times, or may be applied 1 time, or may be applied in combination of a plurality of different ways. Among them, a die coating method excellent in uniform coatability is preferable. In order to avoid contamination with foreign matter, the coating step is preferably performed in an environment where foreign matter is less generated, such as a clean room.

After the resin varnish is applied, the coating is dried in a hot air furnace, a far infrared furnace, or the like as needed. The drying condition is preferably set to 3 to 13 minutes at 80 to 120 ℃. In this manner, the photosensitive resin composition layer is formed on the circuit board.

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

On the other hand, in the case of using a photosensitive film with a support, the photosensitive resin composition layer side is laminated on one surface or both surfaces of the circuit board using a vacuum laminator. In the laminating step, after removing the protective film in the case where the photosensitive film with a support has the protective film, the photosensitive film with a support and the circuit board are preheated as necessary, and the photosensitive resin composition layer is pressed and heated and pressed against the circuit board. For the photosensitive film with a support, a method of laminating the film on a circuit board under reduced pressure by a vacuum lamination method is suitably used.

The lamination conditions are not particularly limited, but for example, the pressure bonding temperature (lamination temperature) is preferably 70 ℃ to 140 ℃, and the pressure bonding pressure is preferably 1kgf/cm²~11kgf/cm²(9.8×10⁴N/m²~107.9×10⁴N/m²) The pressure bonding time is preferably 5 seconds to 300 seconds, and lamination is performed under reduced pressure with an air pressure of 20mmHg (26.7hPa) or less. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum lamination process can be carried out using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum applicators manufactured by ニッコー & マテリアルズ, vacuum pressure laminators manufactured by Nippon Kasei corporation, roll-type dry coaters manufactured by Hitachi インダストリイズ, and vacuum laminators manufactured by Hitachi エーアイーシー.

< step (II) >

An exposure step is performed in which a photosensitive resin composition layer is formed on the circuit board by coating and drying or lamination, and then, active light is irradiated to a predetermined portion of the photosensitive resin composition layer through a mask pattern to photocure the photosensitive resin composition layer in the irradiated portion. Examples of the active light include ultraviolet rays, visible light rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The dose of the ultraviolet ray irradiation was about 10mJ/cm²~1000mJ/cm². The exposure method includes a contact exposure method in which the mask pattern is brought into close contact with the printed wiring board, and a non-contact exposure method in which exposure is performed using parallel light without bringing into close contact with the printed wiring board. When a support is present on the photosensitive resin composition layer, the support may be exposed to light, or the support may be peeled off and then exposed to light.

In step (II), as the mask pattern, for example, a via hole pattern such as a circular hole pattern may be used to form a via hole. The via diameter (opening diameter) is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less. The lower limit is not particularly limited, and may be 1 μm or more and 5 μm or more.

< step (III) >

After the exposure step, when a support is present on the photosensitive resin composition layer, the support is removed and developed, and a portion which is not cured by light (unexposed portion) is removed and developed, whereby a pattern can be formed. Development is typically carried out by wet development.

In the case of the wet development, a safe and stable developer having good workability such as an alkaline aqueous solution, an aqueous developer, an organic solvent, or the like is used as the developer, and among them, a development step using an alkaline aqueous solution is preferable. As the developing method, known methods such as spraying, shaking dipping, Brushing (Brushing), scraping (scraping) and the like can be suitably used.

Examples of the alkaline aqueous solution used as the developer include an aqueous solution of an alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, an aqueous solution of a carbonate or bicarbonate such as sodium carbonate or sodium bicarbonate, an alkali metal phosphate such as sodium phosphate or potassium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate or potassium pyrophosphate, and an aqueous solution of an organic base free from metal ions such as tetraalkylammonium hydroxide, and an aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable in that it does not contain metal ions and does not affect the semiconductor chip.

These alkaline aqueous solutions may contain a surfactant, an antifoaming agent, and the like in order to improve the developing 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 alkali concentration of the alkaline aqueous solution is preferably 0.1 to 10 mass%. The temperature of the alkaline aqueous solution is appropriately selected according to the developability of the photosensitive resin composition layer, and is preferably 20 to 50 ℃.

Examples of the organic solvent used as the developer include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethanol, isopropanol, butanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether.

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

In the pattern formation, the above-mentioned 2 or more developing methods may be used in combination as necessary. Examples of the development method include a dip method, a puddle development method, a spray method, a high-pressure spray method, brushing, scraping, and the like, and the high-pressure spray method is suitable for improving the resolution. The spraying pressure in the case of spraying is preferably 0.05MPa to 0.3 MPa.

< Heat curing (post-baking) step >

After the step (III) is completed, a thermal curing (post-baking) step is performed as necessary to form a solder resist. Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp, and a heating step using a clean oven. When ultraviolet rays are irradiated, the dose can be adjusted as necessary, and can be set to 0.05J/cm, for example²~10J/cm²The irradiation is performed with right and left irradiation amounts. The heating condition may be appropriately selected depending on the kind, content, and the like of the resin component in the photosensitive resin composition, and is preferably selected within a range of from 150 ℃ to 250 ℃ for 20 minutes to 180 minutes, and more preferably within a range of from 160 ℃ to 230 ℃ for 30 minutes to 120 minutes.

< other step >

The printed wiring board may further include a hole opening step and a desmearing step after the solder resist is formed. These steps may be carried out in accordance with various methods known to those skilled in the art used in the manufacture of printed wiring boards.

After the solder resist is formed, a via hole or a through hole is formed by performing a hole opening step on the solder resist formed on the circuit board as desired. The hole-forming step may be performed by a known method such as a drill, a laser, or plasma, or a combination of these methods as necessary, and is preferably performed by a laser such as a carbon dioxide laser or a YAG laser.

The desmear step is a step of performing desmear treatment. Resin residue (drilling smear) generally adheres to the inside of the opening formed in the drilling step. Since the smear causes poor electrical connection, a treatment for removing the smear (desmearing treatment) is performed in this step.

The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

The dry desmear treatment includes, for example, desmear treatment using plasma. The desmear treatment using plasma can be carried out using a commercially available plasma desmear treatment apparatus. Among commercially available plasma desmearing apparatuses, examples suitable for the purpose of manufacturing printed wiring boards include a microwave plasma apparatus manufactured by ニッシン, and an atmospheric pressure plasma etching apparatus manufactured by water-accumulation chemical industry.

As the wet desmear treatment, for example, a desmear treatment using an oxidizing agent solution or the like can be used. In the case of performing desmearing treatment using an oxidizing agent solution, it is preferable to perform swelling treatment using a swelling solution, oxidation treatment using an oxidizing agent solution, and neutralization treatment using a neutralizing solution in this order. Examples of the Swelling liquid include "spinning Dip securigrant P" and "spinning Dip securigrant SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate having the via hole or the like formed therein in a swelling solution heated to 60 to 80 ℃ for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline aqueous solution of permanganic acid, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment using the oxidant solution may be performed by immersing the swelled substrate in the oxidant solution heated to 60 to 80 ℃ for 10 to 30 minutes. Examples of commercially available products of the alkaline permanganate aqueous solution include "コンセントレート & コンパクト CP", "ド - ジングソリューション seed セキュリガンス P" manufactured by Atotech Japan, and the like. The neutralization treatment with the neutralization solution is preferably performed by immersing the substrate after the oxidation treatment in the neutralization solution at 30 to 50 ℃ for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and commercially available products include "リダクションソリューション · セキュリガント P" manufactured by Atotech Japan, inc.

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

In the case where an insulating layer is used as an interlayer insulating layer, the opening step, the desmear step, and the plating step may be performed after the thermosetting step, as in the case of a solder resist.

The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by sputtering after the formation of the insulating layer, may be formed by a combination of electroless plating and electrolytic plating, or may be formed by electroless plating alone, with a plating resist having a pattern reverse to that of the conductor layer. As a method of forming a pattern thereafter, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[ semiconductor device ]

The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, aircrafts, and the like).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that transmits an electrical signal, and may be a surface portion or an embedded portion. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip in the production of the semiconductor device of the present invention is not particularly limited as long as the function of the semiconductor chip is effectively exerted, and specific examples thereof include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bump free build-up layer (BBUL), a mounting method using an Anisotropic Conductive Film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the "mounting method using a bump-less build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board to connect the semiconductor chip and a wiring on the printed wiring board".

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" representing amounts mean "part by mass" and "% by mass", respectively, unless otherwise explicitly indicated.

< example 1 >

A resin composition 1 was obtained by mixing 10 parts by mass of a component (A-1) (manufactured by TR4020G Asahi organic materials Co., Ltd.), 5 parts by mass of a component (A-2) (manufactured by MEHC-7851SS Ming & Chemicals Co., Ltd.), 5 parts by mass of a component (A-3) (manufactured by BisE chemical Co., Ltd.), 5 parts by mass of a compound having at least 2 alkoxymethyl groups in the molecule (manufactured by MW-390 tri and ケミカル Co., Ltd.), 0.05 parts by mass of a photoacid generator (manufactured by MP-triazine tri and ケミカル Co., Ltd.), 6 parts by mass of an organic filler (manufactured by MM-101SM Co., Ltd.) and 12 parts by mass of MEK (manufactured by genuine chemical Co., Ltd.).

MP-triazine has the following structure.

[ solution 37]

< example 2 >

In example 1, the amount of the organic filler ("MM-101 SM" manufactured by Industrial Co., Ltd.) was changed from 6 parts by mass to 2 parts by mass.

In the same manner as in example 1 except for the above matters, resin composition 2 was obtained.

< example 3 >

In example 2,2 parts by mass of an organic filler ("MM-101 SM" manufactured by Kokai Co., Ltd.) was not used.

In the same manner as in example 2 except for the above matters, a resin composition 3 was obtained.

< example 4 >

In example 2, 5 parts by mass of the component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was changed to 5 parts by mass of the component (A-3) ("BisA" manufactured by Mitsui chemical ファイン Co., Ltd.).

In the same manner as in example 2 except for the above matters, a resin composition 4 was obtained.

< example 5 >

In example 2, 5 parts by mass of the component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was changed to 5 parts by mass of the component (A-3) ("BisF" manufactured by Sanjing chemical ファイン Co., Ltd.).

In the same manner as in example 2 except for the above matters, resin composition 5 was obtained.

< example 6 >

In example 2, 5 parts by mass of the component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was changed to 5 parts by mass of the component (A-3) ("BisP-TMC" manufactured by Benzhou chemical Co., Ltd.).

In the same manner as in example 2 except for the above matters, a resin composition 6 was obtained.

< example 7 >

In example 2, 5 parts by mass of the component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was changed to 5 parts by mass of the component (A-3) ("BisP-M" manufactured by Mitsui chemical ファイン Co., Ltd.).

In the same manner as in example 2 except for the above matters, a resin composition 7 was obtained.

< example 8 >

In example 2, 5 parts by mass of the component (A-2) (product of MEHC-7851 SS) was changed to 5 parts by mass of the component (A-2) (product of MEHC-78004S).

In the same manner as in example 2 except for the above matters, a resin composition 8 was obtained.

< example 9 >

In example 2, 30 parts by mass of an inorganic filler ("UFP-30" having an average particle size of 0.3 μm, manufactured by デンカ Co.) was further used.

In the same manner as in example 2 except for the above matters, a resin composition 9 was obtained.

< example 10 >

In example 2, 30 parts by mass of an inorganic filler ("SO-C2" having an average particle size of 0.5 μm, アドマテックス Co.) was used.

In the same manner as in example 2 except for the above matters, a resin composition 10 was obtained.

< example 11 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 4 parts by mass,

the amount of the component (A-2) ("MEHC-7851 SS", manufactured by MEHC Kaisha chemical Co., Ltd.) was changed from 5 parts by mass to 12 parts by mass

The amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 4 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 11 was obtained.

< example 12 >

In the case of the example 2, the following examples were conducted,

the amount of the component (A-2) ("MEHC-7851 SS", manufactured by MEHC Kaisha chemical Co., Ltd.) was changed from 5 parts by mass to 4 parts by mass

The amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 12 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 12 was obtained.

< example 13 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 16 parts by mass,

the amount of the (A-2) component (MEHC-7851 SS, manufactured by MEHC-CHEMICAL CO., LTD.) was changed from 5 parts by mass to 2 parts by mass, and

the amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 2 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 13 was obtained.

< example 14 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 18 parts by mass,

the amount of the component (A-2) ("MEHC-7851 SS", manufactured by MEHC Kaisha chemical Co., Ltd.) was changed from 5 parts by mass to 1 part by mass

The amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 1 part by mass.

In the same manner as in example 2 except for the above matters, a resin composition 14 was obtained.

< example 15 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 2 parts by mass,

The amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 14 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 15 was obtained.

< example 16 >

In the case of the example 2, the following examples were conducted,

the amount of the component (A-2) ("MEHC-7851 SS", manufactured by MEHC Kaisha chemical Co., Ltd.) was changed from 5 parts by mass to 14 parts by mass

In the same manner as in example 2 except for the above matters, a resin composition 16 was obtained.

< comparative example 1 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 20 parts by mass,

5 parts by mass of the (A-2) component (MEHC-7851 SS: manufactured by MIXO CHEMICAL Co.) was not used, and

no 5 parts by mass of component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was used.

In the same manner as in example 2 except for the above matters, a resin composition 17 was obtained.

< comparative example 2 >

In the case of the example 2, the following examples were conducted,

the amount of the component (A-2) ("MEHC-7851 SS", manufactured by MEHC Kaisha chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass

In the same manner as in example 2 except for the above matters, a resin composition 18 was obtained.

< comparative example 3 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed from 5 parts by mass to 10 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 19 was obtained.

< comparative example 4 >

In the case of the example 2, the following examples were conducted,

10 parts by mass of the component (A-1) (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was not used,

In the same manner as in example 2 except for the above matters, a resin composition 20 was obtained.

< comparative example 5 >

In the case of the example 2, the following examples were conducted,

5 parts by mass of the (A-3) component (manufactured by BisE chemical Co., Ltd.) was changed to 5 parts by mass of an alkali-soluble resin (manufactured by TrisP-PA chemical Co., Ltd.) represented by the following structural formula.

In the same manner as in example 2 except for the above matters, a resin composition 21 was obtained.

[ solution 38]

< comparative example 6 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 15 parts by mass,

5 parts by mass of the (A-3) component (BisE, manufactured by Benzhou chemical Co., Ltd.) was changed to 5 parts by mass of an alkali-soluble resin (TrisP-PA, manufactured by Benzhou chemical Co., Ltd.).

In the same manner as in example 2 except for the above matters, a resin composition 22 was obtained.

< comparative example 7 >

In the case of the example 2, the following examples were conducted,

the amount of the (A-1) component (TR 4020G, manufactured by Asahi organic materials Co., Ltd.) was changed from 10 parts by mass to 14 parts by mass,

5 parts by mass of the component (A-2) (MEHC-7851 SS: Ming Kaisha Co., Ltd.) was changed to 6 parts by mass of the component (A-2) (MEHC-78004S: Minisha Kaisha Co., Ltd.),

5 parts by mass of the component (A-3) ("BisE" manufactured by Benzhou chemical Co., Ltd.) was not used,

the amount of the organic filler ("MM-101 SM" manufactured by Kokai industries Co., Ltd.) was changed from 2 parts by mass to 3 parts by mass, and

the amount of a compound having at least 2 alkoxymethyl groups in the molecule (MW-390, manufactured by Sanyo ケミカル Co.) was changed from 5 parts by mass to 6 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 23 was obtained.

< comparative example 8 >

In the case of the example 2, the following examples were conducted,

5 parts by mass of the (A-2) component (MEHC-7851 SS, manufactured by JIAKANG CHEMICAL Co., Ltd.) was not used,

5 parts by mass of the (A-3) component (BisE, manufactured by Benzhou chemical Co., Ltd.) was changed to 4 parts by mass of an alkali-soluble resin (TrisP-PA, manufactured by Benzhou chemical Co., Ltd.), and

the amount of the organic filler ("MM-101 SM" manufactured by Industrial Co., Ltd.) was changed from 2 parts by mass to 3 parts by mass.

In the same manner as in example 2 except for the above matters, a resin composition 24 was obtained.

Production of photosensitive film with support

As a support, a PET film (ルミラー T60, thickness 38 μm, manufactured by east レ corporation) was prepared, and the resin compositions (photosensitive resin compositions) prepared in each of examples and comparative examples were uniformly coated on the PET film by a die coater so that the thickness of the photosensitive resin composition layer after drying became 20 μm, and dried at 80 to 110 ℃ for 6 minutes, thereby obtaining a photosensitive film with a support having a photosensitive resin composition layer on a release PET.

< evaluation of development time dependency >

The copper layer of the glass epoxy substrate (copper-clad laminate) was treated with 5% sulfuric acid. The photosensitive resin composition layer of the photosensitive film with a support was disposed so as to be in contact with the surface of the copper layer, and laminated using a vacuum laminator (VP 160, manufactured by ニッコー & マテリアルズ) to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were sequentially laminated. The pressure bonding conditions were vacuum evacuation time 30 seconds, pressure bonding temperature 80 ℃, pressure bonding pressure 0.7MPa, and pressure time 30 seconds.

The laminate was allowed to stand at room temperature for 30 minutes or more, the support of the laminate was peeled off, and then ultraviolet light (wavelength: 365nm, intensity: 40 mW/cm) was applied using a circular hole pattern and a patterning device²) And (6) carrying out exposure. The developing time was set to 30 seconds, and the exposure amount was 50mJ/cm²To 1000mJ/cm²The range of (2) is appropriately set. The exposure pattern used a quartz glass mask depicting circular holes (vias) with openings of 20 μm. After standing at room temperature for 5 minutes, the support was peeled off from the laminate. The development time was set to 60 seconds, 90 seconds, and 120 seconds, respectively, and the same was performed as in the case where the development time was 30 seconds.

Subsequently, after heat treatment at 80 ℃ for 10 minutes, a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ was sprayed at a spray pressure of 0.1MPa as a developer for 30 seconds, 60 seconds, 90 seconds, and 120 seconds on the entire surface of the photosensitive resin composition layer on the laminate. After spray development, 1J/cm²Further, the photosensitive resin composition layer was cured by heating at 190 ℃ for 60 minutes.

The bottom diameter of the via hole having an opening of 20 μm in the exposure pattern was observed by SEM (magnification 1000 times) for development times of 30 seconds, 60 seconds, 90 seconds, and 120 seconds, and measured. The bottom of the via hole is larger than the opening of the via hole (reverse taper shape)

) In the case where the bottom of the via hole cannot be observed by SEM, the hole is expressed as "inverted cone".

Further, the number of development times at which the bottom diameter of the via hole having an opening of 20 μm of the exposure pattern reached 15 μm or more and 20 μm or less was 4 development times of 30 seconds, 60 seconds, 90 seconds, and 120 seconds (4 of 30 seconds, 60 seconds, 90 seconds, and 120 seconds was the maximum value).

< evaluation of crack resistance (TCT resistance) >

The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit was formed by patterning the copper layer having a thickness of 18 μm was treated with 5% sulfuric acid. The photosensitive film with a support prepared in advance was disposed so that the photosensitive resin composition layer was in contact with the surface of the copper circuit, and was laminated using a vacuum laminator (VP 160, manufactured by ニッコー & マテリアルズ) to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were sequentially laminated. The pressure bonding conditions were vacuum evacuation time 30 seconds, pressure bonding temperature 80 ℃, pressure bonding pressure 0.7MPa, and pressure time 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and exposed to ultraviolet light from the support of the laminate using a circular hole pattern using a patterning device. The exposure pattern was patterned using a mask having openings: a quartz glass mask with circular holes of 10 μm/20 μm/30 μm/40 μm/50 μm/60 μm/70 μm/80 μm/90 μm/100 μm. After standing at room temperature for 5 minutes, the support was peeled off from the laminate. Next, heat treatment was performed at 80 ℃ for 10 minutes. Subsequently, a 2.38 mass% aqueous tetramethylammonium hydroxide solution at 23 ℃ was sprayed and developed as a developing solution at a spray pressure of 0.1MPa for 1 minute over the entire surface of the photosensitive resin composition layer on the laminate. After spray development, 1J/cm²Further, the photosensitive resin composition layer was cured by heating at 190 ℃ for 60 minutes, thereby forming an insulating layer having an opening on the laminate. This was used as a laminate for crack resistance evaluation.

The following tests were carried out: the laminate for crack resistance evaluation was exposed to an atmosphere at-40 ℃ for 15 minutes, then heated at a temperature increase rate of 180 ℃/minute, then exposed to an atmosphere at 160 ℃ for 15 minutes, and then cooled at a temperature decrease rate of 180 ℃/minute, and the above-described heat cycle treatment was repeated 1000 times. In the test, the degree of cracking and peeling of the laminate for crack resistance evaluation was observed by an optical microscope (manufactured by Nikon, "LV-100 ND") after 200 times and 500 times, and evaluated based on the following evaluation criteria.

Very good: no cracks and peeling were observed after 500 times.

O: cracking and peeling were observed after 500 times, but cracking and peeling were not observed after 200 times.

X: cracking and peeling were confirmed after 200 times.

< evaluation of insulation Property (HAST resistance) >

A comb-shaped copper circuit having 6 wiring portions was prepared on a polyimide substrate, the wiring portions having a line width of 15 μm and a space width of 15 μm. Next, the photosensitive resin composition layer of the photosensitive film with a support prepared in advance was disposed so as to be in contact with the surface of the copper circuit, and laminated using a vacuum laminator (VP 160, manufactured by ニッコー and マテリアルズ) to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were sequentially laminated. The pressure bonding conditions were vacuum evacuation time 30 seconds, pressure bonding temperature 80 ℃, pressure bonding pressure 0.7MPa, and pressure time 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and the entire surface of the laminate was exposed to ultraviolet light from the support. The exposure amount at this time is the exposure amount with the best resolution. After standing at room temperature for 5 minutes, the support was peeled off from the laminate. Next, heat treatment was performed at 80 ℃ for 10 minutes. On the entire surface of the photosensitive resin composition layer on the laminate, a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ℃ was spray-developed as a developing solution at a spray pressure of 0.1MPa for 1 minute. After spray development, 1J/cm²Further, the photosensitive resin composition layer was cured by heating at 190 ℃ for 60 minutes, thereby forming an insulating layer having an opening on the laminate. This was used as a laminate for insulation evaluation.

The insulation resistance value of the obtained laminate for insulation evaluation was measured by a resistance measuring machine ("ECM-100" manufactured by J-RAS Co.). Then, the laminate for insulation evaluation was subjected to an environment of 130 ℃ and 85% relative humidity using a HAST tester ("PM 422" manufactured by nakegai chemical corporation), and a voltage of 3.3V was applied to both ends of the electrode. After 100 hours and 200 hours, the laminate for insulation evaluation was taken out, and the insulation resistance value was measured and evaluated based on the following evaluation criteria.

Very good: insulation resistance value after 200 hours is lower than 1 x 10⁷The wiring of Ω is 1 or less among 6 portions

Good: insulation resistance value after 100 hours is lower than 1 x 10⁷The wiring of Ω is 1 or less among 6 portions

X: insulation resistance value after 100 hours is lower than 1 x 10⁷The wiring of Ω is2 or more among 6 portions.

In the table, the content of the component (A-1) means the content of the component (A-1) based on 100 mass% of the whole component (A). The content of the component (A-2) is the content of the component (A-2) based on 100 mass% of the whole component (A). The content of the component (A-3) is the content of the component (A-3) based on 100 mass% of the whole component (A).

From the results of the above table, it is understood that the number of development times (4 of 30 seconds, 60 seconds, 90 seconds, and 120 seconds) for which the bottom diameter of the via hole in examples 1 to 16 is 15 μm or more and 20 μm or less is larger than that in comparative examples 1 to 8. From this, it is clear that examples 1 to 16 are excellent in stability against the developer even if the developing time is prolonged. Therefore, in examples 1 to 16, even if the thickness of the photosensitive resin composition layer varied, the bottom diameter of the via hole could be made uniform.

In addition, it is clear that examples 1 to 16 are also superior in crack resistance and insulating properties to comparative examples 1 to 8.

In each example, even when the components (D) and (E) were not contained, the results were confirmed to be similar to those in the above examples, although there was a certain difference.

Claims

1. A photosensitive resin composition comprising:

(A) an alkali-soluble resin having a phenolic hydroxyl group in the molecule,

(C) a photo-acid generating agent,

(A) comprises the following components: a compound having a structure represented by the following formula (A-1), a compound having a structure represented by the formula (A-2), and a compound having a structure represented by the formula (A-3),

[ solution 1]

in the formula (A-3), R³Represents a 2-valent group represented by the following formula (a), a 2-valent group represented by the following formula (b), and the following formula (c) A 2-valent group shown, or a 2-valent group formed by a combination thereof, X³And X⁴Each independently represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, a halogen atom, or a 1-valent heterocyclic group optionally having a substituent; n3 and n4 each independently represent an integer of 0 to 4;

[ solution 2]

2. The photosensitive resin composition according to claim 1, wherein the content of the compound having a structure represented by formula (A-1) is 5% by mass or more and 85% by mass or less based on 100 parts by mass of the entire component (A).

3. The photosensitive resin composition according to claim 1, wherein the content of the compound having a structure represented by formula (A-2) is 6 to 80 mass% based on 100 parts by mass of the entire component (A).

4. The photosensitive resin composition according to claim 1, wherein the content of the compound having the structure represented by formula (A-3) is 6% by mass or more and 80% by mass or less based on 100 parts by mass of the entire component (A).

5. The photosensitive resin composition according to claim 1, further comprising any one of (D) an organic filler, and (E) an inorganic filler.

6. The photosensitive resin composition according to claim 1, wherein the component (B) contains an amino resin having at least 2 alkoxymethyl groups in the molecule.

7. The photosensitive resin composition according to claim 1, wherein the component (B) contains a melamine resin.

8. A photosensitive film with a support, comprising: a support, and a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 provided on the support.

9. A printed wiring board comprising an insulating layer formed from a cured product of the photosensitive resin composition according to any one of claims 1 to 7.

10. The printed wiring board according to claim 9, wherein the insulating layer is a solder resist.

11. A semiconductor device comprising the printed wiring board according to claim 9 or 10.

12. A method for manufacturing a printed wiring board, comprising:

a step of forming a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 7 on a circuit board,

And a step of developing the cured photosensitive resin composition layer.