Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board

Abstract

To provide a photosensitive resin composition, a photosensitive resin composition for photo via formation, and a photosensitive resin composition for interlayer insulating layer, each of which is excellent in both photosensitive characteristics and strippability from a support film, to provide a photosensitive resin film and a photosensitive resin film for interlayer insulating layer, each of which is composed of the photosensitive resin composition, to provide a multilayer printed wiring board and a semiconductor package, and to provide a method for producing the multilayer printed wiring board.SOLUTION: A photosensitive resin composition comprises (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting resin, where (A) the photopolymerizable compound having the ethylenically unsaturated group includes (A1) a photopolymerizable compound having an acidic substituent and an alicyclic structure together with an ethylenically unsaturated group, and one of the raw materials of (A1) the photopolymerizable compound having the ethylenically unsaturated group is (a1) an alicyclic skeleton-containing epoxy resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a multilayer printed wiring board and a semiconductor package, and a method for producing a multilayer printed wiring board. [Background technology]

[0002] In recent years, electronic devices have become smaller and more powerful, and multilayer printed wiring boards are becoming increasingly dense due to an increase in the number of circuit layers and finer wiring. In particular, the density of semiconductor package substrates, such as BGA (ball grid array) and CSP (chip size package), on which semiconductor chips are mounted, has increased significantly, and in addition to finer wiring, thinner insulating films and smaller diameter vias (also called "via holes") for interlayer connection are required.

[0003] One method for manufacturing a printed wiring board is a build-up method (see, for example, Patent Document 1) in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated to form a multilayer printed wiring board. As circuits become finer, the semi-additive method in which circuits are formed by plating has become mainstream for multilayer printed wiring boards. In conventional semi-additive processes, for example, (1) a thermosetting resin film is laminated onto a conductor circuit, and the thermosetting resin film is cured by heating to form an "interlayer insulating layer." (2) Next, vias for interlayer connection are formed by laser processing, and desmearing and roughening treatments are performed using alkaline permanganate or the like. (3) After that, electroless copper plating is performed on the substrate, and a pattern is formed using a resist, followed by electrolytic copper plating to form a copper circuit layer. (4) Next, the resist is stripped, and the electroless layer is flash etched to form the copper circuit.

[0004] As mentioned above, laser processing is the mainstream method for forming vias in an interlayer insulating layer formed by curing a thermosetting resin film, but the reduction in the diameter of vias by laser irradiation using a laser processing machine has reached its limit. Furthermore, when forming vias using a laser processing machine, each via hole must be formed one by one, and when a large number of vias are required for high density, forming the vias takes a long time, resulting in poor manufacturing efficiency.

[0005] Under these circumstances, a method has been proposed as a method capable of forming a large number of vias at once, in which a photosensitive resin composition containing (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound is used, in which the content of the inorganic filler (D) is 10 to 80 mass %, and multiple small-diameter vias are formed at once by photolithography (see, for example, Patent Document 2).

[0006] Patent Document 2 addresses the problem of suppressing the decrease in adhesive strength with plated copper that occurs when a photosensitive resin composition is used instead of a conventional thermosetting resin composition as a material for an interlayer insulating layer or a surface protective layer. It also addresses the problems of via resolution and adhesion to silicon substrates and chip components, and claims to have solved these problems. However, photosensitive resin films (dry films) formed from conventional photosensitive resin compositions tend to have a high peel strength from the support film. Therefore, when the photosensitive resin film with the support film is thermally transferred onto a substrate while being pressed onto the substrate using a laminator, the photosensitive layer forming the photosensitive resin film may partially remain on the support film. If this occurs, defects may occur in the image pattern (vias) formed on the photosensitive resin film by photolithography, which may result in a decrease in via resolution.

[0007] A known method for solving such problems is to add a release agent to a photosensitive resin composition (see, for example, paragraph

[0078] of Patent Document 3). While the addition of a release agent certainly improves the releasability between the photosensitive layer and the support film, this method makes it difficult to achieve both releasability from the support film and photosensitivity. Specifically, it is known that if the amount of release agent added to the photosensitive layer is small, the releasability from the support film becomes insufficient, while if the amount of release agent added is increased, the photosensitive properties such as the sensitivity and resolution of the photosensitive layer tend to decrease (see, for example, paragraph

[0010] of Patent Document 4). Therefore, there is a strong demand for the development of a photosensitive resin composition that achieves both photosensitivity and releasability from the support film. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-304931 [Patent Document 2] Japanese Patent Application Publication No. 2017-116652 [Patent Document 3] Special Publication No. 2008-529080 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-226148 Summary of the Invention [Problem to be solved by the invention]

[0009] Therefore, an object of the present invention is to provide a photosensitive resin composition, a photosensitive resin composition for forming photovias, and a photosensitive resin composition for an interlayer insulating layer, which are excellent in both photosensitivity and releasability from a support film. It is also an object of the present invention to provide a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer, each made of the photosensitive resin composition, a multilayer printed wiring board, a semiconductor package, and a method for producing the multilayer printed wiring board. [Means for solving the problem]

[0010] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a photosensitive resin composition containing the below-described components (A) to (C), in which the component (A) contains "(A1) a photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton," and the thermosetting resin (C) further contains a predetermined amount of (C1) a thermosetting resin having an alicyclic skeleton.

[0011] That is, the present invention relates to the following [1] to

[19] . [1] A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting resin, a photosensitive resin composition, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group comprises (A1) a photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton; and the (C) thermosetting resin comprises (C1) a thermosetting resin having an alicyclic skeleton, and the content of the (C1) component is 10 parts by mass or more per 100 parts by mass of the (A) component. [2] The photosensitive resin composition according to [1] above, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group further comprises at least one selected from the group consisting of (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. [3] The photosensitive resin composition according to the above [1] or [2], wherein in both the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, and the (C1) thermosetting resin having an alicyclic skeleton, the alicyclic skeleton is an alicyclic skeleton having 5 to 20 ring carbon atoms. [4] The photosensitive resin composition according to the above [1] or [2], wherein in both the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, and the (C1) thermosetting resin having an alicyclic skeleton, the alicyclic skeleton comprises two or more rings. [5] The photosensitive resin composition according to the above [1], [2] or [4], wherein in both the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, and the (C1) thermosetting resin having an alicyclic skeleton, the alicyclic skeleton consists of three rings. [6] The photosensitive resin composition according to any one of the above [1] to [5], wherein in both the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, and the (C1) thermosetting resin having an alicyclic skeleton, the alicyclic skeleton is represented by the following general formula (a): [ka] (In general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. 1 is an integer between 0 and 6. * is a binding site to another structure. [7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton is represented by the following general formula (A-1): [ka] (In general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A2 represents an alkyl group having 1 to 12 carbon atoms. A3 is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R A3 is an organic group having an ethylenically unsaturated group and an acidic substituent. A1 is an integer between 0 and 6, m A2 is an integer between 0 and 3. A1 is between 0 and 10.) [8] The photosensitive resin composition according to any one of the above [1] to [7], wherein in the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, the acidic substituent is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group. [9] The photosensitive resin composition according to any one of the above [1] to [8], wherein the (C1) thermosetting resin having an alicyclic skeleton is represented by the following general formula (C-1): [ka] (In general formula (C-1), R C1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. C2 represents an alkyl group having 1 to 12 carbon atoms. C1 is an integer between 0 and 6, m C2 is an integer between 0 and 3. C1 is between 0 and 10.)

[10] The photosensitive resin composition according to any one of the above [1] to [9], further comprising (F) an inorganic filler.

[11] The photosensitive resin composition according to any one of the above [1] to

[10] , further comprising (G) a curing agent.

[12] A photosensitive resin composition for forming a photovia hole, comprising the photosensitive resin composition according to any one of [1] to

[11] above.

[13] A photosensitive resin composition for an interlayer insulating layer, comprising the photosensitive resin composition according to any one of [1] to

[11] above.

[14] A photosensitive resin film comprising the photosensitive resin composition according to any one of the above [1] to

[11] .

[15] A photosensitive resin film for an interlayer insulating layer, which comprises the photosensitive resin composition according to any one of the above [1] to

[11] .

[16] A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of the above [1] to

[11] .

[17] A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film described in

[14] above.

[18] A semiconductor package comprising the multilayer printed wiring board according to

[16] or

[17] above and a semiconductor element mounted thereon.

[19] A method for producing a multilayer printed wiring board, comprising the following steps (1) to (4): Step (1): A step of laminating the photosensitive resin film described in

[14] above onto one or both sides of a circuit board. Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1). Step (3): A step of roughening the via and the interlayer insulating layer. Step (4): forming a circuit pattern on the interlayer insulating layer. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive resin composition for forming photovias, and a photosensitive resin composition for an interlayer insulating layer, which are excellent in both photosensitivity and releasability from a support film. It is also possible to provide a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer, which are made of the photosensitive resin composition, and a multilayer printed wiring board and a semiconductor package, which include an interlayer insulating layer formed using the photosensitive resin composition or the photosensitive resin film. Furthermore, it is possible to provide a method for efficiently manufacturing a multilayer printed wiring board having high-resolution vias. The vias in the multilayer printed wiring board obtained by the manufacturing method of the present invention can have a smaller diameter than vias formed by laser processing. [Brief explanation of the drawings]

[0013] [Figure 1] 2A to 2C are schematic diagrams illustrating an example of a manufacturing process for a multilayer printed wiring board according to the present embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the numerical ranges described herein, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. In addition, the lower and upper limit of a numerical range may be arbitrarily combined with the lower or upper limit of another numerical range. Furthermore, in this specification, when there are multiple substances corresponding to each component in the photosensitive resin composition, the content of each component means the total content of the multiple substances present in the photosensitive resin composition, unless otherwise specified. As used herein, the term "number of ring carbon atoms" refers to the number of carbon atoms necessary to form a ring, and does not include the number of carbon atoms of substituents (e.g., methyl groups) that the ring has. For example, in both a cyclohexane skeleton and a methylcyclohexane skeleton, the number of ring carbon atoms is 6. Additionally, the present invention also includes embodiments in which the descriptions in this specification are combined in any desired manner.

[0015] [Photosensitive resin composition, photosensitive resin composition for forming photovias, and photosensitive resin composition for interlayer insulating layer] A photosensitive resin composition according to one embodiment of the present invention (hereinafter may be simply referred to as this embodiment) is a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting resin, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group comprises (A1) a photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton, and the (C) thermosetting resin comprises (C1) a thermosetting resin having an alicyclic skeleton, and the content of the (C1) component is 10 parts by mass or more per 100 parts by mass of the (A) component. In this specification, the components may be referred to as component (A), component (B), component (A1), component (C), etc., and similar abbreviations may be used for other components. In this specification, the term "resin component" refers to the components (A) to (C), etc., and includes other components that may be included as needed (e.g., components (D), (E), and (H)), but does not include the inorganic filler (F) and pigment (G), which may be included as needed, as described below. Furthermore, the term "solid content" refers to the nonvolatile content of the photosensitive resin composition excluding volatile substances such as water and solvents. It refers to the components that remain without volatilization when the resin composition is dried, and also includes liquid, starch syrup-like, and wax-like substances at room temperature around 25°C.

[0016] The photosensitive resin composition of this embodiment is suitable for via formation by photolithography (also referred to as photovia formation), and therefore the present invention also provides a photosensitive resin composition for photovia formation. Furthermore, the photosensitive resin composition of this embodiment has excellent photosensitivity and peelability from the support film, and also has excellent electrical insulation reliability, making it useful as an interlayer insulating layer in a multilayer printed wiring board. Therefore, the present invention also provides a photosensitive resin composition for an interlayer insulating layer. In this specification, the term "photosensitive resin composition" includes photosensitive resin compositions for photovia formation and photosensitive resin compositions for an interlayer insulating layer. The photosensitive resin composition of this embodiment is useful as a negative photosensitive resin composition. Each component that the photosensitive resin composition may contain will be described in detail below.

[0017] <(A) Photopolymerizable Compound Having an Ethylenically Unsaturated Group> The photosensitive resin composition of this embodiment contains a photopolymerizable compound having an ethylenically unsaturated group as component (A). Examples of the ethylenically unsaturated group contained in component (A) include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group. The ethylenically unsaturated group is preferably a (meth)acryloyl group. In the present invention, the component (A) contains the photopolymerizable compound (A1) described below, which has an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton. In order to achieve both photosensitive properties and releasability from the support film, it is important that the component (A) contains at least the component (A1). The component (A1) will be described in detail below.

[0018] ((A1) Photopolymerizable Compound Having an Ethylenically Unsaturated Group, an Acidic Substituent, and an Alicyclic Skeleton) Examples of the ethylenically unsaturated group contained in the component (A1) include the same ethylenically unsaturated groups as those described above, and are preferably at least one selected from the group consisting of a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth)acryloyl group, more preferably a vinyl group, an allyl group, or a (meth)acryloyl group, and even more preferably a (meth)acryloyl group. The acidic substituent contained in the component (A1) is preferably at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, and the like, with a carboxyl group being more preferred.

[0019] From the viewpoints of photosensitive properties and releasability from the support film, the alicyclic skeleton of the component (A1) is preferably an alicyclic skeleton having 5 to 20 ring carbon atoms, more preferably an alicyclic skeleton having 5 to 18 ring carbon atoms, still more preferably an alicyclic skeleton having 6 to 18 ring carbon atoms, particularly preferably an alicyclic skeleton having 8 to 14 ring carbon atoms, and most preferably an alicyclic skeleton having 8 to 12 ring carbon atoms. From the viewpoints of photosensitive properties and releasability from the support film, the alicyclic skeleton preferably consists of two or more rings, more preferably two to four rings, and even more preferably three rings. Examples of alicyclic skeletons consisting of two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a saturated dicyclopentadiene skeleton. As the alicyclic skeleton, a saturated dicyclopentadiene skeleton is preferred from the viewpoint of photosensitive properties and releasability from the support film, and an alicyclic skeleton (saturated dicyclopentadiene skeleton) represented by the following general formula (a) is more preferred. [ka] (In general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A1 is an integer between 0 and 6. * is a binding site to another structure.

[0020] In the general formula (a), R A1 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. m A1 is an integer of 0 to 6, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and even more preferably 0. m A1 If is 2 or more, multiple R A1 may be the same or different. A1 may be substituted on the same carbon atom or on different carbon atoms, to the extent possible. * denotes a bonding site to another structure, and may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to a carbon atom represented by 1 or 2 and a carbon atom represented by either 3 or 4 in the following general formula (a'). [ka] (In general formula (a'), R A1 , m A1 and * are the same as those in general formula (a).

[0021] From the viewpoints of alkaline development, photosensitive properties, and releasability from a support film, the component (A1) is preferably an "(A1-1) acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative" obtained by reacting (a1) an alicyclic skeleton-containing epoxy resin modified with (a2) an ethylenically unsaturated group-containing organic acid [hereinafter, sometimes referred to as component (A')] with (a3) ​​a saturated group- or unsaturated group-containing polybasic acid anhydride.

[0022] -(a1) Alicyclic skeleton-containing epoxy resin- The (a1) alicyclic skeleton-containing epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0023] In the present invention, the epoxy resin used is at least an epoxy resin having an alicyclic skeleton, which is explained in the same manner as the alicyclic skeleton of component (A1) described above, and preferred embodiments are also the same. The (a1) alicyclic skeleton-containing epoxy resin is preferably an epoxy resin represented by the following general formula (a1-1): Also preferred is an epoxy resin having a structural unit represented by the following general formula (a1-2): [ka] (In general formula (a1-1), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A2 represents an alkyl group having 1 to 12 carbon atoms. A1 is an integer between 0 and 6, m A2 is an integer between 0 and 3. A1 is between 0 and 10.) [ka] (In general formula (a1-2), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A1 is an integer between 0 and 6.)

[0024] In the general formula (a1-1) and the general formula (a1-2), R A1 is R in the general formula (a) A1 The preferred embodiments are also the same. R in general formula (a1-1) A2 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. m in general formula (a1-1) and general formula (a1-2) A1 is m in the general formula (a) A1 The preferred embodiments are also the same. m in general formula (a1-1) A2 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. n in general formula (a1-1) A1 represents the repeating number of the structural unit in the parentheses, and is between 0 and 10. Usually, epoxy resins are mixtures of structural units with different repeating numbers in the parentheses, so in that case, n A1 is expressed as the average value of the mixture. A1 is preferably 2 to 10.

[0025] As the (a1) alicyclic skeleton-containing epoxy resin, a commercially available product may be used, and examples of commercially available products include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200HH, and EPICLON HP-7200HHH (trade names, manufactured by DIC Corporation, "EPICLON" is a registered trademark), and the like.

[0026] As the (a1) epoxy resin, epoxy resins other than the epoxy resin having an alicyclic skeleton (hereinafter, sometimes referred to as other epoxy resins) may be used in combination. Examples of other epoxy resins include bisphenol-based epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; bisphenol-based novolac-type epoxy resins such as bisphenol A novolac-type epoxy resins and bisphenol F novolac-type epoxy resins; novolac-type epoxy resins other than the bisphenol-based novolac-type epoxy resins, such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, and biphenyl novolac-type epoxy resins; phenol aralkyl-type epoxy resins; biphenyl aralkyl-type epoxy resins; stilbene-type epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthalene-type epoxy resins, naphthol novolac-type epoxy resins, naphthol-type epoxy resins, naphthol aralkyl-type epoxy resins, and naphthylene ether-type epoxy resins; biphenyl-type epoxy resins; xylylene-type epoxy resins; dihydroanthracene-type epoxy resins; aliphatic linear epoxy resins; and rubber-modified epoxy resins.

[0027] -(a2) Ethylenically unsaturated group-containing organic acid- The (a2) ethylenically unsaturated group-containing organic acid is not particularly limited, but is preferably an ethylenically unsaturated group-containing monocarboxylic acid. The ethylenically unsaturated group is as described above for the ethylenically unsaturated group in component (A1). Examples of the ethylenically unsaturated group-containing monocarboxylic acid include acrylic acid; acrylic acid derivatives such as acrylic acid dimers, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid; half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides; and half-ester compounds which are reaction products of ethylenically unsaturated group-containing monoglycidyl ethers or ethylenically unsaturated group-containing monoglycidyl esters and dibasic acid anhydrides. Among these, acrylic acid is preferred. The component (a2) may be used alone or in combination of two or more.

[0028] The half-ester compound can be obtained, for example, by reacting a hydroxyl group-containing acrylate, an ethylenically unsaturated group-containing monoglycidyl ether, or an ethylenically unsaturated group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio.

[0029] Examples of the hydroxyl group-containing acrylate, ethylenically unsaturated group-containing monoglycidyl ether, and ethylenically unsaturated group-containing monoglycidyl ester used in the synthesis of the semi-ester compound, which is an example of component (a2), include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.

[0030] The dibasic acid anhydride used in the synthesis of the half-ester compound may contain a saturated group or an unsaturated group, and examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0031] Although not particularly limited, the reaction between the (a1) component and the (a2) component is preferably carried out at a ratio of 0.6 to 1.05 equivalents of the (a2) component per equivalent of the epoxy group in the (a1) component, or may be carried out at a ratio of 0.8 to 1.0 equivalents. By carrying out the reaction at such a ratio, photopolymerization is improved, i.e., photosensitivity increases, and photosensitive properties, particularly via resolution, tend to improve.

[0032] The component (a1) and the component (a2) can be dissolved in an organic solvent and reacted. Examples of organic solvents include ketones such as methyl ethyl 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 acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0033] Furthermore, it is preferable to use a catalyst to promote the reaction between the component (a1) and the component (a2). Examples of the catalyst include amine catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltrimethylammonium iodide; and phosphine catalysts such as triphenylphosphine. Among these, phosphine catalysts are preferred, and triphenylphosphine is more preferred. The amount of catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the total of the components (a1) and (a2). This amount tends to promote the reaction between the components (a1) and (a2).

[0034] In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, or pyrogallol. When a polymerization inhibitor is used, the amount used is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 parts by mass, and even more preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the total of the (a1) component and the (a2) component, from the viewpoint of improving the storage stability of the composition.

[0035] The reaction temperature between the component (a1) and the component (a2) is preferably 60 to 150°C, more preferably 70 to 120°C, and even more preferably 80 to 120°C, from the viewpoint of productivity.

[0036] In this way, it is presumed that the component (A') obtained by reacting the component (a1) with the component (a2) has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of the component (a1) and the carboxyl group of the component (a2).

[0037] -(a3) Polybasic acid anhydride- The component (a3) ​​may contain either a saturated group or an unsaturated group. Examples of the component (a3) ​​include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferred from the viewpoint of photosensitive properties.

[0038] It is presumed that by further reacting the component (A') obtained above with the component (a3) ​​containing a saturated or unsaturated group, the hydroxyl groups of component (A') (including the hydroxyl groups originally present in component (a1)) and the acid anhydride groups of component (a3) ​​are semi-esterified to form an acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative (A1-1).

[0039] In the reaction of component (A') with component (a3), for example, the acid value of the acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative (A1-1) can be adjusted by reacting 0.1 to 1.0 equivalents of component (a3) ​​with 1 equivalent of hydroxyl groups in component (A'). The acid value of the (A1-1) acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative is preferably 30 to 150 mgKOH / g, more preferably 40 to 120 mgKOH / g, and even more preferably 50 to 100 mgKOH / g. If the acid value is 30 mgKOH / g or more, the photosensitive resin composition tends to have excellent solubility in dilute alkaline solutions, and if it is 150 mgKOH / g or less, the electrical properties of the cured film tend to be improved.

[0040] The reaction temperature between the component (A') and the component (a3) ​​is preferably 50 to 150°C, more preferably 60 to 120°C, and even more preferably 70 to 100°C, from the viewpoint of productivity.

[0041] In view of the above, the (A1) photopolymerizable compound having an ethylenically unsaturated group as well as an acidic substituent and an alicyclic skeleton is not particularly limited, but is preferably represented by the following general formula (A-1). [ka] (In general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A2 represents an alkyl group having 1 to 12 carbon atoms. A3is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R A3 is an organic group having an ethylenically unsaturated group and an acidic substituent. A1 is an integer between 0 and 6, m A2 is an integer between 0 and 3. A1 is between 0 and 10.)

[0042] R in the general formula (A-1) A1 , R A2 , m A1 , m A2 and n A1 is the same as in the general formula (a1-1), and the preferred values ​​are also the same. R A3 is as defined above, but corresponds to the moiety formed by the reaction of the glycidyl group in the general formula (a1-1) with the component (a2) and the component (a3), and this definition takes into consideration that some of the glycidyl group may remain unreacted. A3 The "organic group having an ethylenically unsaturated group" is a group derived from the (a2) component, and the "organic group having an ethylenically unsaturated group and an acidic substituent" is a group derived from the (a2) and (a3) ​​components. If the (a2) and (a3) ​​components react with all the glycidyl groups in the general formula (a1-1), R A3 is an "organic group having an ethylenically unsaturated group and an acidic substituent," whereas the portion that has reacted only with component (a2) is an "organic group having an ethylenically unsaturated group," and the portion that has not reacted with either component (a2) or component (a3) ​​is a "glycidyl group."

[0043] ((A1) Molecular Weight of Photopolymerizable Compound Having an Ethylenically Unsaturated Group, an Acidic Substituent, and an Alicyclic Skeleton) The weight-average molecular weight (Mw) of component (A1) is preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 18,000. Within this range, photosensitive properties and releasability from the support film are improved. In particular, the weight-average molecular weight (Mw) of the acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative (A1-1) is preferably within the above range. Herein, the weight-average molecular weight is a value measured by gel permeation chromatography (GPC) (manufactured by Tosoh Corporation) using a calibration curve of standard polystyrene, and more specifically, a value measured according to the method described below. <Method for measuring weight average molecular weight> The weight-average molecular weight was measured using the GPC measurement device and measurement conditions described below, and the value converted using a calibration curve of standard polystyrene was used as the weight-average molecular weight. The calibration curve was created using a set of five standard polystyrene samples ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation). (GPC measurement device) GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: TSKgel SuperMultipore HZ-H column (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measurement conditions) Solvent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35mL / min Sample concentration: 10 mg / 5 mL of THF Injection volume: 20μL

[0044] ((A2-1) Acid-modified ethylenically unsaturated group-containing epoxy derivatives not containing an alicyclic skeleton) The (A) photopolymerizable compound having an ethylenically unsaturated group may further include "(A2-1) an acid-modified ethylenically unsaturated group-containing epoxy derivative not containing an alicyclic skeleton," which is obtained by reacting a compound obtained by modifying (a21) an epoxy resin (but not containing an alicyclic skeleton) with (a22) an ethylenically unsaturated group-containing organic acid with (a23) a saturated group- or unsaturated group-containing polybasic acid anhydride, or may not include the component (A2-1).

[0045] The epoxy resin (a21) is not particularly limited as long as it is an epoxy resin that does not contain an alicyclic skeleton, and examples thereof include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred. The (a21) epoxy resins are further classified into various epoxy resins depending on the main skeleton, and each of the above types of epoxy resins is further classified as follows: Specifically, they are classified into bisphenol-based epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; bisphenol-based novolac-type epoxy resins such as bisphenol A novolac-type epoxy resin and bisphenol F novolac-type epoxy resin; novolac-type epoxy resins other than the above-mentioned bisphenol-based novolac-type epoxy resins, such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, and biphenyl novolac-type epoxy resin; phenol aralkyl-type epoxy resins; stilbene-type epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthalene-type epoxy resin, naphthol novolac-type epoxy resin, naphthol-type epoxy resin, naphthol aralkyl-type epoxy resin, and naphthylene ether-type epoxy resin; biphenyl-type epoxy resin; biphenyl aralkyl-type epoxy resin; xylylene-type epoxy resin; dihydroanthracene-type epoxy resin; aliphatic linear epoxy resin; and rubber-modified epoxy resins.

[0046] The (a22) ethylenically unsaturated group-containing organic acid and the (a23) saturated or unsaturated group-containing polybasic acid anhydride are explained in the same manner as the (a2) ethylenically unsaturated group-containing organic acid and the (a3) ​​saturated or unsaturated group-containing polybasic acid anhydride, and preferred embodiments are also the same. Furthermore, as a method for reacting the compound obtained by modifying the component (a21) with the component (a22) with the component (a23), reference can be made to a method for reacting the compound obtained by modifying the component (a1) with the component (a2) with the component (a3).

[0047] (A2-1) As the acid-modified ethylenically unsaturated group-containing epoxy derivative not containing an alicyclic skeleton, commercially available products may be used, and examples of commercially available products include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185, ZCR-1569H, ZXR-1807, ZCR-6000, ZCR-8000 (all of which are product names manufactured by Nippon Kayaku Co., Ltd.), UE-9000, UE-EXP-2810PM, and UE-EXP-3045 (all of which are product names manufactured by DIC Corporation).

[0048] ((A2-2) Styrene-maleic acid resin) As the (A) photopolymerizable compound having an ethylenically unsaturated group, a "(A2-2) styrene-maleic acid resin" such as a hydroxyethyl (meth)acrylate-modified styrene-maleic anhydride copolymer can also be used in combination. The (A2-2) component does not contain an alicyclic skeleton. The (A2-2) component may be used alone or in combination of two or more.

[0049] ((A2-3) Epoxy-based polyurethane resin) Furthermore, as the (A) photopolymerizable compound having an ethylenically unsaturated group, a compound obtained by modifying the (a21) epoxy resin with an (a22) ethylenically unsaturated group-containing organic acid, i.e., component (A'), can be used in combination with an "epoxy polyurethane resin (A2-3)" obtained by reacting this compound with an isocyanate compound. The (A2-3) component does not contain an alicyclic skeleton. One type of component (A2-3) may be used alone, or two or more types may be used in combination.

[0050] (Component (A) other than the above) From the viewpoint of improving chemical resistance after curing (exposure) and increasing the difference in developer resistance between exposed and unexposed areas, the (A) photopolymerizable compound having an ethylenically unsaturated group preferably further comprises at least one selected from the group consisting of (Ai) monofunctional vinyl monomers having one polymerizable ethylenically unsaturated group, (Aii) bifunctional vinyl monomers having two polymerizable ethylenically unsaturated groups, and (Aiii) multifunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups, and more preferably comprises component (Aiii). Components (Ai) to (Aiii) preferably have a molecular weight of 1,000 or less. However, in the present invention, components (Ai) to (Aiii) do not include component (A1).

[0051] ((Ai) Monofunctional vinyl monomer) Examples of the monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group include (meth)acrylic acid and (meth)acrylic acid alkyl esters. Examples of the (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, and (meth)acrylic acid hydroxylethyl ester. The component (Ai) may be used alone or in combination of two or more.

[0052] ((Aii) Bifunctional vinyl monomer) Examples of the bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups include polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane, bisphenol A diglycidyl ether di(meth)acrylate, etc. One type of component (Aii) may be used alone, or two or more types may be used in combination.

[0053] ((Aiii) Multifunctional vinyl monomer) Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include (meth)acrylate compounds having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri(meth)acrylate; (meth)acrylate compounds having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from pentaerythritol, such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate; (meth)acrylate compounds having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate; (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane, such as ditrimethylolpropane tetra(meth)acrylate; and (meth)acrylate compounds having a skeleton derived from diglycerin. Among these, from the viewpoint of improving chemical resistance after curing (exposure) and increasing the difference in developer resistance between exposed and unexposed areas, (meth)acrylate compounds having a skeleton derived from dipentaerythritol are preferred, and dipentaerythritol penta(meth)acrylate is more preferred. The component (Aiii) may be used alone or in combination of two or more. Here, the "(meth)acrylate compound having a skeleton derived from XXX" (where XXX is the name of the compound) means an esterification product of XXX and (meth)acrylic acid, and the esterification product also includes a compound modified with an alkyleneoxy group.

[0054] (Content of component (A)) The content of component (A) is not particularly limited, but from the viewpoints of heat resistance, electrical properties, and chemical resistance, it is preferably 5 to 80 mass %, more preferably 10 to 75 mass %, even more preferably 25 to 75 mass %, and particularly preferably 45 to 70 mass %, based on the total solid content of the photosensitive resin composition.

[0055] Although the component (A) is not particularly limited, it is preferable to use the component (A1) and the component (Aiii) in combination from the viewpoint of photosensitivity. In this case, the content ratio of the component (A1) to the component (Aiii) [(A1) / (Aiii)] (mass ratio) is preferably 2 to 20, more preferably 4 to 15, even more preferably 6 to 13, particularly preferably 8 to 12, and most preferably 8 to 11. Furthermore, the content of component (A1) relative to the total amount of component (A) is preferably 20 to 95 mass%, more preferably 40 to 90 mass%, even more preferably 45 to 80 mass%, and particularly preferably 50 to 70 mass%, from the viewpoints of photosensitive characteristics, adhesive strength with plated copper, and electrical insulation reliability.

[0056] <(B) Photopolymerization initiator> The component (B) used in this embodiment is not particularly limited as long as it can polymerize the component (A), and can be appropriately selected from commonly used photopolymerization initiators. Examples of component (B) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-methyl-1-[4-(methylthio)methyl]-1-propanol ... (e) Acetophenones such as phenyl-2-morpholino-1-propanone and N,N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone thioxanthones such as acetophenone dimethyl ketal, benzil dimethyl ketal, and other ketals; benzophenones such as benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, and 4-benzoyl-4'-methyldiphenyl sulfide; acridines such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; bis(2,4,6- acylphosphine oxides such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyloxime), 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime], and the like.Among these, acetophenones, acylphosphine oxides, and oxime esters are preferred, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) are more preferred. Acetophenones have the advantage of being less volatile and less likely to be released as outgassing, acylphosphine oxides have the advantage of being easily cured to the bottom, and oxime esters have the advantage of being easily cured on the surface. The component (B) may be used alone or in combination of two or more. When two or more are used in combination, acetophenones, acylphosphine oxides, and oxime esters are preferably used in combination, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) are more preferably used in combination.

[0057] ((B) Component Content) The content of component (B) is not particularly limited, but is preferably 0.1 to 15 mass%, more preferably 0.15 to 5 mass%, even more preferably 0.2 to 3 mass%, and particularly preferably 0.5 to 2 mass%, based on the total solid content of the photosensitive resin composition. If the content of component (B) is 0.1 mass% or more, the risk of elution of exposed portions during development in an interlayer insulating layer formed using the photosensitive resin composition tends to be reduced, and if it is 15 mass% or less, heat resistance tends to be improved.

[0058] <(B') Photopolymerization initiation aid> The photosensitive resin composition of this embodiment may contain (B') a photopolymerization initiation aid in addition to the component (B). Examples of the (B') photopolymerization initiation aid include tertiary amines such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. One type of component (B') may be used alone, or two or more types may be used in combination. When the photosensitive resin composition of this embodiment contains the component (B'), the content thereof is preferably 0.01 to 20 mass%, more preferably 0.2 to 5 mass%, and even more preferably 0.3 to 2 mass%, based on the total amount of resin components in the photosensitive resin composition. Note that the photosensitive resin composition of this embodiment does not necessarily contain the component (B').

[0059] <(C) Thermosetting resin> The photosensitive resin composition of this embodiment contains a thermosetting resin as component (C). Component (C) does not include anything equivalent to component (A), and in that respect, it can be said that component (C) does not contain an ethylenically unsaturated group. Furthermore, any substance that satisfies the above conditions and has an epoxy group is also included in component (C). By including a thermosetting resin (C) in the photosensitive resin composition of this embodiment, in addition to improving the adhesive strength with plated copper and the insulation reliability, heat resistance tends to be improved. In particular, the photosensitive resin composition of this embodiment includes, as the thermosetting resin (C), a thermosetting resin having an alicyclic skeleton (C1), and the content of the component (C1) is 10 parts by mass or more per 100 parts by mass of the component (A). This configuration allows for both excellent photosensitivity and releasability from the support film. From the same perspective, the content of the component (C1) is preferably 10 to 40 parts by mass, more preferably 10 to 35 parts by mass, and may be 13 to 35 parts by mass, 15 to 35 parts by mass, or 20 to 35 parts by mass per 100 parts by mass of the component (A).

[0060] As in the case of the component (A1), from the viewpoints of photosensitive properties and releasability from the support film, the alicyclic skeleton of the component (C1) is preferably an alicyclic skeleton having 5 to 20 ring carbon atoms, more preferably an alicyclic skeleton having 5 to 18 ring carbon atoms, still more preferably an alicyclic skeleton having 6 to 18 ring carbon atoms, particularly preferably an alicyclic skeleton having 8 to 14 ring carbon atoms, and most preferably an alicyclic skeleton having 8 to 12 ring carbon atoms. As in the case of the component (A1), from the viewpoints of photosensitive properties and releasability from the support film, the alicyclic skeleton preferably consists of two or more rings, more preferably two to four rings, and even more preferably three rings. Examples of alicyclic skeletons consisting of two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a saturated dicyclopentadiene skeleton. As the alicyclic skeleton, a saturated dicyclopentadiene skeleton is preferred from the viewpoint of photosensitive properties and releasability from the support film, and an alicyclic skeleton (saturated dicyclopentadiene skeleton) represented by the following general formula (c) is more preferred. [ka] (In general formula (c), R C1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. C1 is an integer between 0 and 6. * is a binding site to another structure.

[0061] In the general formula (c), R C1 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. m C1 is an integer of 0 to 6, preferably an integer of 0 to 5, more preferably an integer of 0 to 2, and even more preferably 0. m C1 If is 2 or more, multiple RC1 may be the same or different. C1 may be substituted on the same carbon atom or on different carbon atoms, to the extent possible. * denotes a bonding site to another structure, and may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to a carbon atom represented by 1 or 2 and a carbon atom represented by either 3 or 4 in the following general formula (c'): [ka] (In general formula (c'), R C1 , m C1 and * are the same as those in general formula (c).

[0062] Examples of thermosetting resins include epoxy resins, phenolic resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. Furthermore, the thermosetting resin is not particularly limited to these, and any known thermosetting resin can be used. Among these, epoxy resins are preferred. Among these, those having an alicyclic skeleton are classified as component (C1), and those without an alicyclic skeleton are classified as component (C2). The component (C) may be used alone or in combination of two or more types.

[0063] The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0064] Epoxy resins are also classified into various epoxy resins depending on the main skeleton, and each of the above types of epoxy resins is further classified as follows: Specifically, bisphenol-based epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; bisphenol-based novolac-type epoxy resins such as bisphenol A-type novolac-type epoxy resins and bisphenol F-type novolac-type epoxy resins; novolac-type epoxy resins other than the above bisphenol-based novolac-type epoxy resins, such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, and biphenyl novolac-type epoxy resins; phenol aralkyl-type epoxy resins; stilbene-type epoxy resins; and naphthalene-type epoxy resins. Epoxy resins are classified into naphthalene skeleton-containing epoxy resins such as naphthol novolac epoxy resins, naphthol epoxy resins, naphthol aralkyl epoxy resins, and naphthylene ether epoxy resins; biphenyl epoxy resins; biphenyl aralkyl epoxy resins; xylylene epoxy resins; dihydroanthracene epoxy resins; alicyclic skeleton-containing epoxy resins such as dicyclopentadiene epoxy resins; heterocyclic epoxy resins; spiro ring-containing epoxy resins; cyclohexanedimethanol epoxy resins; trimethylol epoxy resins; aliphatic linear epoxy resins; and rubber-modified epoxy resins. The component (C) may be used alone or in combination of two or more types.

[0065] Among these, dicyclopentadiene-type epoxy resins are preferred as component (C1) from the viewpoints of photosensitive properties and releasability from the support film, and bisphenol-based epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, and naphthylene ether-type epoxy resins are preferred as component (C2) from the viewpoints of heat resistance, electrical insulation reliability, and adhesive strength with plated copper, with biphenyl-type epoxy resins being more preferred. Commercially available epoxy resins can also be used, including, for example, bisphenol A epoxy resins (manufactured by Mitsubishi Chemical Corporation under the names "jER828EL" and "YL980"), bisphenol F epoxy resins (manufactured by Mitsubishi Chemical Corporation under the names "jER806H" and "YL983U"), naphthalene epoxy resins (manufactured by DIC Corporation under the names "HP4032D" and "HP4710"), naphthalene skeleton-containing multifunctional epoxy resins (manufactured by Nippon Kayaku Co., Ltd. under the name "NC7000"), naphthol epoxy resins (manufactured by Nippon Steel Chemical & Examples of epoxy resins that can be used include epoxy resins having a biphenyl structure ("NC3000H" and "NC3500" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins having a biphenyl structure ("YX4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation), anthracene-type epoxy resins ("YX8800" manufactured by Mitsubishi Chemical Corporation), glycerol-type epoxy resins ("ZX1542" manufactured by Nippon Steel Chemical & Material Co., Ltd.), and naphthylene ether-type epoxy resins ("EXA7311-G4" manufactured by DIC Corporation).

[0066] As the component (C1), an epoxy resin represented by the following general formula (C-1) or an epoxy resin represented by the following general formula (C-2) is particularly preferred, and an epoxy resin represented by the following general formula (C-1) is more preferred. [ka] (In general formula (C-1), R C1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. C2 represents an alkyl group having 1 to 12 carbon atoms. C1 is an integer between 0 and 6, m C2 is an integer between 0 and 3. C1 is between 0 and 10.) [ka] (In general formula (C-2), R C1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. C1is an integer between 0 and 6.)

[0067] In the general formula (C-1) and the general formula (C-2), R C1 is R in the general formula (c) C1 The preferred embodiments are also the same. R in general formula (C-1) C2 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. m in general formula (C-1) and general formula (C-2) C1 is m in the general formula (c) C1 The preferred embodiments are also the same. m in general formula (C-1) C2 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. n in general formula (C-1) C1 represents the repeating number of the structural unit in the parentheses, and is between 0 and 10. Usually, epoxy resins are mixtures of structural units with different repeating numbers in the parentheses, so in that case, n C1 is expressed as the average value of the mixture. C1 is preferably 2 to 10.

[0068] As the component (C1), a commercially available product may be used, and examples of commercially available products include XD-1000 (trade name, manufactured by Nippon Kayaku Co., Ltd.), EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200HH, and EPICLON HP-7200HHH (trade names, manufactured by DIC Corporation, "EPICLON" is a registered trademark), etc.

[0069] When the photosensitive resin composition of the present embodiment contains the component (C2) in addition to the component (C1), the content ratio [component (C1) / component (C2)] (mass ratio) is not particularly limited, but from the viewpoints of photosensitive properties and releasability from the support film, it is preferably 55 / 45 to 95 / 5, more preferably 60 / 40 to 90 / 10, even more preferably 70 / 30 to 90 / 10, and particularly preferably 75 / 25 to 85 / 15.

[0070] Furthermore, in addition to the above-mentioned examples, epoxy-modified polybutadiene can also be used as the epoxy resin. In particular, from the viewpoint of handleability during the production of printed wiring boards, component (C) may be a combination of an aromatic epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature, such as epoxy-modified polybutadiene.

[0071] The epoxy-modified polybutadiene preferably has hydroxyl groups at the molecular terminals, more preferably at both molecular terminals, and even more preferably at only both molecular terminals. The number of hydroxyl groups in the epoxy-modified polybutadiene is not particularly limited as long as it is one or more, but is preferably 1 to 5, more preferably 1 or 2, and even more preferably 2. From the viewpoints of adhesive strength with plated copper, heat resistance, thermal expansion coefficient, and flexibility, the epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (C-3).

[0072] [ka] (In the above formula (C-3), a, b, and c each represent the ratio of the structural units in the parentheses, where a is 0.05 to 0.40, b is 0.02 to 0.30, and c is 0.30 to 0.80, and further, a+b+c=1.00 and (a+c)>b are satisfied. y represents the number of structural units in the square brackets and is an integer of 10 to 250.)

[0073] In the general formula (C-3), the structural units in the square brackets may be bonded in any order. In other words, the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right may be interchanged, and if they are represented as (a), (b), and (c), respectively, various bonding orders are possible, such as -[(a)-(b)-(c)]-[(a)-(b)-(c)-]-, -[(a)-(c)-(b)]-[(a)-(c)-(b)-]-, -[(b)-(a)-(c)]-[(b)-(a)-(c)-]-, -[(a)-(b)-(c)]-[(c)-(b)-(a)-]-, -[(a)-(b)-(a)]-[(c)-(b)-(c)-]-, -[(c)-(b)-(c)]-[(b)-(a)-(a)-]-, and -[(b)-(c)]-[(b)-(a)-(a)-]-. From the viewpoints of adhesive strength with plated copper, heat resistance, thermal expansion coefficient, and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.40 to 0.80. From the same viewpoints, y is preferably an integer of 30 to 180.

[0074] In the general formula (C-3), a=0.20, b=0.20, c=0.60, and y=an integer of 10 to 250, and examples of commercially available epoxidized polybutadiene include "Epolead (registered trademark) PB3600" (manufactured by Daicel Corporation).

[0075] ((C) Component Content) The content of component (C) in the photosensitive resin composition of this embodiment is not particularly limited, but is preferably 5 to 70 mass %, more preferably 5 to 40 mass %, even more preferably 7 to 30 mass %, and particularly preferably 10 to 20 mass %, based on the total solids content of the photosensitive resin composition. When the content of component (C) is 5 mass % or more, sufficient crosslinking of the photosensitive resin composition is obtained, and the adhesive strength to plated copper and the electrical insulation reliability tend to be improved. On the other hand, when the content is 70 mass % or less, the photosensitive characteristics tend to be good. As mentioned above, when the component (C) contains the component (C1) in the above-mentioned amount, it is possible to achieve both good photosensitive properties and good releasability from the support film.

[0076] <(D) Elastomer> The photosensitive resin composition of this embodiment may contain an elastomer as component (D). By including component (D), the photosensitive resin composition tends to have excellent photosensitivity, adhesive strength with plated copper, and electrical insulation reliability. Component (D) also has the effect of suppressing a decrease in flexibility and adhesive strength with plated copper, which is caused by strain (internal stress) within the cured product due to cure shrinkage of component (A). Component (D) is preferably an elastomer that is liquid at 25°C. The component (D) may be used alone or in combination of two or more types.

[0077] Examples of elastomers include styrene-based elastomers, olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers, and it is preferable to use at least one selected from these. These elastomers are composed of a hard segment component and a soft segment component, the former of which tends to contribute to heat resistance and strength, and the latter of which tends to contribute to flexibility and toughness. Among the above examples, component (D) preferably contains at least one selected from the group consisting of olefin elastomers, polyester elastomers, and urethane elastomers, from the viewpoints of compatibility, solubility, and adhesive strength with plated copper.Moreover, component (D) is more preferably at least one selected from the group consisting of olefin elastomers, polyester elastomers, and urethane elastomers.

[0078] (styrene elastomer) Examples of the styrene elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, etc. One type of styrene elastomer may be used alone, or two or more types may be used in combination. Examples of components constituting the styrene-based elastomer include styrene; and styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene. The styrene elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 3,000 to 20,000. In this specification, the number average molecular weight is a value determined in terms of standard polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. Commercially available styrene elastomers can also be used.

[0079] (olefin elastomer) The olefin elastomer is, for example, a polymer or copolymer of an α-olefin having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, or 4-methylpentene. The olefin elastomer may have a hydroxyl group at the molecular end, and preferably has a hydroxyl group at the molecular end. One type of olefin elastomer may be used alone, or two or more types may be used in combination. Suitable examples of olefin-based elastomers include polyethylene, polybutadiene, hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisopropylene, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), etc. Also included are copolymers of the above-mentioned α-olefins having 2 to 20 carbon atoms with non-conjugated dienes having 2 to 20 carbon atoms, such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and isoprene. Further examples include carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer. The olefin elastomer preferably has a number average molecular weight of 1,000 to 8,000, more preferably 1,000 to 6,500, even more preferably 1,000 to 5,000, and particularly preferably 1,500 to 3,500. Commercially available olefin elastomers can also be used.

[0080] (Polyester elastomer) The polyester elastomer may be obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. One type of polyester elastomer may be used alone, or two or more types may be used in combination. Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; aromatic dicarboxylic acids in which hydrogen atoms on the aromatic ring of the aromatic dicarboxylic acid are substituted with methyl groups, ethyl groups, phenyl groups, and the like; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. From the viewpoint of adhesion to the substrate, it is also preferable to use dimer acids derived from natural products as the dicarboxylic acid. One type of dicarboxylic acid may be used alone, or two or more types may be used in combination. Examples of the derivatives of the dicarboxylic acids include anhydrides of the dicarboxylic acids.

[0081] Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; and aromatic diols represented by the following general formula (D-1): One type of diol compound may be used alone, or two or more types may be used in combination.

[0082] [ka] (In general formula (D-1), X D1 represents an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, or -SO2-. D1 and R D2 each independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms; p and q each independently represents an integer of 0 to 4, and r is 0 or 1.

[0083] In general formula (D-1), X D1 Examples of the alkylene group having 1 to 10 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. From the viewpoints of photosensitivity characteristics, adhesive strength with plated copper, and electrical insulation reliability, the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group. X D1 Examples of the alkylidene group having 2 to 10 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. As the alkylidene group, an isopropylidene group is preferred from the viewpoints of photosensitivity, adhesive strength with plated copper, and electrical insulation reliability. X D1 Examples of the cycloalkylene group having 4 to 8 carbon atoms represented by include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group. X D1Among the above, alkylene groups having 1 to 10 carbon atoms and alkylidene groups having 2 to 10 carbon atoms are preferred, and methylene and isopropylidene groups are more preferred.

[0084] In general formula (D-1), R D1 and R D2 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R D1 and R D2 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. p and q each independently represent an integer of 0 to 4, and are each preferably 0 or 1. r may be either 0 or 1, but when r is 0, the structure is represented by the following general formula (D-1'). [ka] (In general formula (D-1'), X D1 , R D1 and p are the same as those in general formula (D-1), and the preferred embodiments are also the same.

[0085] Examples of the aromatic diol represented by the general formula (D-1) include bisphenol A, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)propane, and resorcinol.

[0086] Furthermore, as the polyester-based elastomer, a multi-block copolymer in which an aromatic polyester (e.g., polybutylene terephthalate) portion serves as a hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion serves as a soft segment component can also be used, and it is preferable to use such a multi-block copolymer.

[0087] The polyester elastomer preferably has a number average molecular weight of 900 to 30,000, more preferably 1,000 to 25,000, and even more preferably 5,000 to 20,000. The polyester elastomer may be a commercially available product.

[0088] (urethane elastomer) Suitable examples of the urethane elastomer include those containing a hard segment composed of a short-chain diol and a diisocyanate, and a soft segment composed of a polymeric (long-chain) diol and a diisocyanate. One type of urethane elastomer may be used alone, or two or more types may be used in combination. Examples of the polymeric (long-chain) diol include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-hexylene carbonate), poly(1,6-hexylene-neopentylene adipate), etc. The number average molecular weight of the polymeric (long-chain) diol is preferably 500 to 10,000. Examples of the short-chain diol include ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A. The number average molecular weight of the short-chain diol is preferably 48-500. The urethane elastomer preferably has a number average molecular weight of 1,000 to 25,000, more preferably 1,500 to 20,000, and even more preferably 2,000 to 15,000. The urethane elastomer may be a commercially available product.

[0089] (Polyamide elastomer) Polyamide elastomers are broadly divided into two types: polyether block amides, which use polyamides for the hard segments and polyethers for the soft segments; and polyether ester block amides, which use polyamides for the hard segments and polyesters for the soft segments. Specific examples of the polyamide elastomer include block copolymers having polyamide as a hard segment component and polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, polymethacrylate, polyurethane, silicone rubber, etc. One type of polyamide elastomer may be used alone, or two or more types may be used in combination. The polyamide elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000. The polyamide elastomer may be a commercially available product.

[0090] (acrylic elastomer) Examples of the acrylic elastomer include polymers of raw material monomers containing acrylic acid esters as the main component. Suitable examples of acrylic acid esters include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, and ethoxyethyl acrylate. Furthermore, the cross-linking monomer may be a copolymer of glycidyl methacrylate, allyl glycidyl ether, or the like, and may further be a copolymer of acrylonitrile, ethylene, or the like. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer. One type of acrylic elastomer may be used alone, or two or more types may be used in combination. The acrylic elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000.

[0091] (Silicone elastomer) The silicone elastomer is an elastomer containing organopolysiloxane as a main component, and is classified into, for example, polydimethylsiloxane elastomers, polymethylphenylsiloxane elastomers, polydiphenylsiloxane elastomers, etc. One type of silicone elastomer may be used alone, or two or more types may be used in combination. The silicone elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000. As the silicone elastomer, a commercially available product may be used.

[0092] (Other elastomers) In addition, the component (D) may be at least one selected from the group consisting of polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone resin, tetrafluoroethylene resin, polyacrylonitrile resin, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.

[0093] ((D) Component Content) When the photosensitive resin composition of this embodiment contains component (D), the content thereof is preferably 0.5 to 20 mass%, more preferably 1 to 20 mass%, even more preferably 1 to 15 mass%, particularly preferably 1 to 10 mass%, and most preferably 1 to 6 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (D) is 0.5 mass% or more, the effect of improving adhesive strength with plated copper is sufficient, and electrical insulation reliability also tends to be excellent. When the content of component (D) is 20 mass% or less, photosensitivity characteristics, adhesive strength with plated copper, and electrical insulation reliability tend to be good.

[0094] <(E) Thermal polymerization initiator> The photosensitive resin composition of this embodiment may contain a thermal polymerization initiator as the component (E). The thermal polymerization initiator is not particularly limited, and examples thereof include hydroperoxides such as diisopropylbenzene hydroperoxide "Percumyl P" (trade name, manufactured by NOF Corporation (hereinafter the same)), cumene hydroperoxide "Percumyl H", and t-butyl hydroperoxide "Perbutyl H"; α,α-bis(t-butylperoxy-m-isopropyl)benzene "Perbutyl P", dicumyl peroxide "Percumyl D", 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane "Perhexa 25B", t-butylcumyl peroxide "Perbutyl C", and di-t-butyl peroxide "Perbutyl D". Examples of peroxides include dialkyl peroxides such as 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 "Perhexyne 25B" and t-butylperoxy-2-ethylhexanoate "Perbutyl O"; ketone peroxides; peroxyketals such as n-butyl 4,4-di-(t-butylperoxy)valerate "Perhexa V"; diacyl peroxides; peroxydicarbonates; organic peroxides such as peroxyesters; and azo compounds such as 2,2'-azobisisobutylnitrile, 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile). Among these, dialkyl peroxides are preferred, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 is more preferred, from the viewpoint of not inhibiting photopolymerization and having a significant effect of improving the physical properties and characteristics of the photosensitive resin composition. The thermal polymerization initiator may be used alone or in combination of two or more kinds.

[0095] (Content of component (E)) When the photosensitive resin composition of this embodiment contains component (E), its content is not particularly limited, but is preferably 0.01 to 5 mass%, more preferably 0.02 to 3 mass%, and even more preferably 0.03 to 2 mass%, based on the total amount of resin components in the photosensitive resin composition. If it is 0.01 mass% or more, sufficient thermal curing tends to be achieved, and if it is 5 mass% or less, photosensitivity characteristics and heat resistance tend to be good.

[0096] <(F) Inorganic filler> The photosensitive resin composition of this embodiment may contain, and preferably contains, an inorganic filler as component (F). The inclusion of an inorganic filler allows for low thermal expansion and reduces the risk of warping. While thermosetting resin compositions conventionally used as interlayer insulating layers in multilayer printed wiring boards have been reduced in thermal expansion by incorporating inorganic fillers, incorporating inorganic fillers into photosensitive resin compositions can cause light scattering and hinder development. While incorporating inorganic fillers presents new challenges unique to photosensitive resin compositions, the photosensitive resin composition of this embodiment tends to have good photosensitivity even when incorporating inorganic fillers. Therefore, the photosensitive resin composition of this embodiment can achieve both low thermal expansion and excellent photosensitivity.

[0097] Examples of the (F) component include silica (SiO2), alumina (Al2O3), titania (TiO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO·TiO2), barium carbonate (BaCO3), magnesium carbonate (MgCO3), aluminum hydroxide (Al(OH)3), magnesium hydroxide (Mg(OH)2), lead titanate (PbO·TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO·Al2O 3), mullite (3Al2O3·2SiO2), cordierite (2MgO·2Al2O3 / 5SiO2), talc (3MgO·4SiO2·H2O), aluminum titanate (TiO2·Al2O3), yttria-containing zirconia (Y2O3·ZrO2), barium silicate (BaO·8SiO2), boron nitride (BN), calcium carbonate (CaCO3), barium sulfate (BaSO4), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO·TiO2), hydrotalcite, mica, calcined kaolin, carbon, etc. Component (F) can be used alone or in combination of two or more.

[0098] From the viewpoint of photosensitivity, the average particle size of component (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, even more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm. Here, the average particle size of component (F) refers to the volume-average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows: First, the photosensitive resin composition is diluted (or dissolved) 1,000 times with methyl ethyl ketone, and then particles dispersed in the solvent are measured using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321 at a refractive index of 1.38. The particle size at 50% cumulative value (volume-based) in the particle size distribution is taken as the average particle size (volume-average particle size). Furthermore, the component (F) contained in the photosensitive resin film and the interlayer insulating layer provided on the support film can also be measured using the submicron particle analyzer after diluting (or dissolving) the component 1,000 times (volume ratio) using a solvent as described above.

[0099] From the viewpoints of heat resistance and low thermal expansion, component (F) preferably contains silica, and more preferably is silica. Furthermore, component (F) may be surface-treated with alumina or an organosilane compound from the viewpoint of improving the dispersibility of the inorganic filler in the photosensitive resin composition by preventing aggregation.

[0100] ((F) Component Content) When the photosensitive resin composition of this embodiment contains component (F), its content is not particularly limited, but is preferably 5 to 80 mass%, more preferably 5 to 60 mass%, even more preferably 8 to 45 mass%, particularly preferably 10 to 30 mass%, and most preferably 10 to 20 mass%, based on the total solid content of the photosensitive resin composition. When the content of component (F) is within the above range, mechanical strength, heat resistance, low thermal expansion, photosensitivity, etc. can be improved.

[0101] <(G) Pigment> The photosensitive resin composition of this embodiment may contain a pigment as component (G) depending on the desired color in order to adjust photosensitivity, etc. As component (G), a colorant that develops the desired color may be appropriately selected and used, and preferred examples thereof include known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

[0102] ((G) Component Content) When the photosensitive resin composition of the present embodiment contains the component (G), the content thereof is preferably 0.01 to 15 mass %, more preferably 0.1 to 12 mass %, and even more preferably 3 to 10 mass %, based on the total solid content of the photosensitive resin composition, from the viewpoint of adjusting photosensitivity, etc.

[0103] <(H) Hardener> The photosensitive resin composition of this embodiment may contain a curing agent from the viewpoint of further improving various properties such as heat resistance, adhesive strength with plated copper, chemical resistance, etc. In particular, when the (C) thermosetting resin contains an epoxy resin, it is preferable that the curing agent contains an epoxy resin curing agent. Examples of component (H) include imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, and polybasic hydrazides; organic acid salts and / or epoxy adducts thereof; amine complexes of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl) tertiary amines such as m-aminophenol, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinylphenol, brominated polyvinylphenol, phenol novolac, and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above-mentioned polybasic acid anhydrides; and diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrylium hexafluorophosphate. Among these, polyamines are preferred, and melamine is more preferred, from the viewpoint of further improving various properties such as heat resistance, adhesive strength to plated copper, and chemical resistance. When the photosensitive resin composition of the present embodiment contains the component (H), the content thereof is preferably 0.01 to 30 mass%, more preferably 0.1 to 25 mass%, even more preferably 5 to 25 mass%, and particularly preferably 10 to 25 mass%, based on the total solid content of the photosensitive resin composition.

[0104] <Diluent> A diluent can be used in the photosensitive resin composition of this embodiment, if necessary. Examples of the diluent include organic solvents. Examples of the organic solvent include ketones such as methyl ethyl 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 acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The diluents may be used alone or in combination of two or more.

[0105] (Diluent content) The content of the diluent may be appropriately selected so that the concentration of the total solid content in the photosensitive resin composition is preferably 40 to 90 mass%, more preferably 50 to 80 mass%, even more preferably 55 to 70 mass%, and particularly preferably 55 to 65 mass%. By adjusting the amount of the diluent used in this manner, the coatability of the photosensitive resin composition is improved, and it becomes possible to form a more precise pattern.

[0106] <Other additives> The photosensitive resin composition of this embodiment may contain, as necessary, various known and commonly used additives such as polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; and silane coupling agents. Furthermore, the composition may contain flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, phosphate compounds of antimony compounds and phosphorus-based compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters.

[0107] The photosensitive resin composition of this embodiment can be obtained by kneading and mixing the components using a roll mill, a bead mill, or the like. Here, the photosensitive resin composition of the present embodiment may be used in the form of a liquid or a film. When used in a liquid form, the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include various application methods such as printing, spin coating, spray coating, jet dispensing, inkjet coating, dip coating, etc. Among these, from the viewpoint of more easily forming a photosensitive layer, the printing method or spin coating method may be appropriately selected. When used in the form of a film, it can be used, for example, in the form of a photosensitive resin film described later, and in this case, a photosensitive resin film with a support film having a photosensitive layer of a desired thickness can be formed by laminating it on a support film using a laminator, etc. Note that use in the form of a film is preferred because it increases the production efficiency of multilayer printed wiring boards.

[0108] [Photosensitive resin film, photosensitive resin film for interlayer insulation layer] The photosensitive resin film of the present embodiment is a photosensitive layer that will later become an interlayer insulating layer and is made of the photosensitive resin composition of the present embodiment. The photosensitive resin film of the present embodiment may be in a form in which the photosensitive resin film is provided on a support film. The thickness (thickness after drying) of the photosensitive resin film (photosensitive layer) is not particularly limited, but from the viewpoint of thinning the multilayer printed wiring board, it is preferably 1 to 100 μm, more preferably 1 to 50 μm, and even more preferably 5 to 40 μm.

[0109] The photosensitive resin film of the present embodiment can be obtained, for example, by applying the photosensitive resin composition of the present embodiment onto a support film using a known coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, and drying the applied composition, thereby forming a photosensitive layer that will later become an interlayer insulating layer. The support film is not particularly limited, but examples thereof include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; and polyolefin films such as polypropylene film and polyethylene film. Among these, polyester film is preferred, and polyethylene terephthalate film is more preferred. The thickness of the support film may be appropriately selected from the range of 5 to 100 μm, but is preferably 5 to 60 μm, and more preferably 15 to 45 μm.

[0110] Furthermore, the photosensitive resin film of this embodiment may have a protective film provided on the surface of the photosensitive layer opposite to the surface in contact with the support film. As the protective film, for example, a polymer film such as polyethylene or polypropylene may be used. Furthermore, the same polymer film as the support film described above may be used, or a different polymer film may be used.

[0111] The coating film formed by applying the photosensitive resin composition can be dried using a dryer that uses hot air drying, far infrared rays, or near infrared rays. The drying temperature is preferably 60 to 150°C, more preferably 70 to 120°C, and even more preferably 80 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes. The content of the remaining diluent in the photosensitive resin film after drying is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of preventing the diluent from diffusing during the manufacturing process of a multilayer printed wiring board.

[0112] The photosensitive resin film of this embodiment has excellent photosensitivity and peelability from the support film, making it suitable as an interlayer insulating layer for a multilayer printed wiring board. That is, the present invention also provides a photosensitive resin film for an interlayer insulating layer. The photosensitive resin film for an interlayer insulating layer can also be called an interlayer insulating photosensitive film.

[0113] [Multilayer printed wiring board and its manufacturing method] The present invention also provides a multilayer printed wiring board containing an interlayer insulating layer formed using the photosensitive resin composition or photosensitive resin film of the present embodiment. The multilayer printed wiring board of the present embodiment can be easily produced by any method, as long as it includes a step of forming an interlayer insulating layer using the photosensitive resin composition of the present embodiment. For example, the multilayer printed wiring board can be easily produced by the following method of producing a multilayer printed wiring board of the present embodiment.

[0114] Hereinafter, as an example of a preferred embodiment of the method for manufacturing a multilayer printed wiring board, a method for manufacturing a multilayer printed wiring board using the photosensitive resin film of this embodiment (photosensitive resin film for interlayer insulating layer) will be described with reference to Figure 1 as appropriate. Multilayer printed wiring board 100A can be manufactured, for example, by a manufacturing method including the following steps (1) to (4). Step (1): A step of laminating the photosensitive resin film of the present embodiment onto one or both sides of a circuit board (hereinafter referred to as "laminating step (1)"). Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1) (hereinafter referred to as "photovia forming step (2)"). Step (3): A step of roughening the via and the interlayer insulating layer (hereinafter referred to as "roughening step (3)"). Step (4): A step of forming a circuit pattern on the interlayer insulating layer (hereinafter referred to as "circuit pattern forming step (4)").

[0115] (Lamination process (1)) The laminating step (1) is a step of laminating the photosensitive resin film of this embodiment (photosensitive resin film for interlayer insulating layer) onto one or both sides of a circuit board (substrate 101 having circuit pattern 102) using a vacuum laminator. Examples of vacuum laminators include a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a roll-type dry coater manufactured by Hitachi, Ltd., and a vacuum laminator manufactured by Hitachi Chemical Electronics Co., Ltd.

[0116] When a protective film is provided on the photosensitive resin film, the protective film can be peeled off or removed, and then the photosensitive resin film can be laminated by pressing it onto the circuit board while applying pressure and heat so that the photosensitive resin film is in contact with the circuit board. The lamination can be carried out, for example, after preheating the photosensitive resin film and the circuit board as necessary, at a pressure of 70 to 130°C, a pressure of 0.1 to 1.0 MPa, and a reduced pressure of 20 mmHg (26.7 hPa) or less, but is not particularly limited to these conditions. The lamination method may be a batch method or a continuous method using a roll. Finally, the photosensitive resin film (hereinafter sometimes referred to as the photosensitive layer) laminated to the circuit board is cooled to about room temperature to form the interlayer insulating layer 103. The support film may be peeled off at this point, or may be peeled off after exposure as described below.

[0117] (Photovia formation process (2)) In the photovia forming step (2), at least a portion of the photosensitive resin film laminated to the circuit board is exposed to light and then developed. The exposed portion is photocured to form a pattern. The exposure method is not particularly limited, and may be, for example, a method of irradiating the active light imagewise through a negative or positive mask pattern known as artwork (mask exposure method), or a method of irradiating the active light imagewise by a direct imaging exposure method such as LDI (Laser Direct Imaging) exposure or DLP (Digital Light Processing) exposure. Known light sources can be used as the light source for actinic rays. Specific examples of light sources include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and lasers that effectively emit ultraviolet or visible light, such as semiconductor lasers. The exposure dose is appropriately selected depending on the light source used and the thickness of the photosensitive layer. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is usually 10 to 1,000 mJ / cm for a photosensitive layer with a thickness of 1 to 100 μm. 2 The preferred range is 15 to 500 mJ / cm 2 is more preferred.

[0118] In the development, the uncured portions of the photosensitive layer are removed from the substrate, and an interlayer insulating layer made of a photocured product is formed on the substrate. When a support film is present on the photosensitive layer, the support film is removed before removing (developing) the unexposed portion. The development method includes wet development and dry development, either of which may be used, but wet development is widely used and can also be used in this embodiment. In the case of wet development, development is carried out by a known development method using a developer suitable for the photosensitive resin composition. Examples of development methods include dipping, bathing, spraying, brushing, slapping, scraping, and swinging immersion. Among these, from the viewpoint of improving resolution, the spraying method is preferred, and among the spraying methods, the high-pressure spraying method is more preferred. Development may be carried out by one method, or by combining two or more methods. The composition of the developer is appropriately selected depending on the composition of the photosensitive resin composition. Examples include alkaline aqueous solutions, water-based developers, and organic solvent-based developers, and among these, alkaline aqueous solutions are preferred.

[0119] In the photovia forming process (2), after exposure and development, 200 to 10,000 mJ / cm 2 (preferably 500 to 5,000 mJ / cm 2 The interlayer insulating layer may be further cured, and it is preferable to perform post-UV curing with an exposure amount of 1000 ppm or less, and post-thermal curing at a temperature of about 60 to 250°C (preferably 120 to 200°C) as needed. In this manner, an interlayer insulating layer having vias 104 is formed. There are no particular limitations on the shape of the vias, and examples of cross-sectional shapes include a rectangle and an inverted trapezoid (the upper side is longer than the lower side), and examples of shapes viewed from the front (the direction from which the via bottom is visible) include a circle and a rectangle. In the formation of vias by photolithography in this embodiment, it is possible to form vias having a cross-sectional shape of an inverted trapezoid (the upper side is longer than the lower side), which is preferable because it improves the adhesion of plated copper to the via wall surface.

[0120] The size (diameter) of the via formed by this process can be less than 40 μm, and can even be 30 μm or less, 20 μm or less, or 10 μm or less, and is particularly advantageous in that it can be 5 μm or less. In this way, the diameter can be made smaller than the size of vias formed by laser processing. There is no particular lower limit to the size (diameter) of the via formed by this process, but it may be 15 μm or more, or 20 μm or more. However, the size (diameter) of the vias formed in this step is not necessarily limited to less than 40 μm, and may be, for example, about 200 μm or less, or may be arbitrarily selected within the range of, for example, 15 to 300 μm.

[0121] (Roughening treatment step (3)) In the roughening treatment step (3), the surfaces of the vias and the interlayer insulating layer are roughened with a roughening liquid. If smears occur in the photovia formation step (2), the smears may be removed with the roughening liquid. The roughening treatment and smear removal can be performed simultaneously. Examples of the roughening solution include a chromium / sulfuric acid roughening solution, an alkaline permanganate roughening solution (for example, a sodium permanganate roughening solution), and a sodium fluoride / chromium / sulfuric acid roughening solution. The roughening treatment forms uneven anchors on the surface of the via and the interlayer insulating layer.

[0122] (Circuit pattern formation process (4)) The circuit pattern forming step (4) is a step of forming a circuit pattern on the interlayer insulating layer after the roughening treatment step (3). From the viewpoint of forming fine wiring, the circuit pattern is preferably formed by a semi-additive process, which forms the circuit pattern and also establishes via conduction. In the semi-additive process, first, the via bottom, via wall, and entire surface of the interlayer insulating layer after the roughening treatment step (3) are subjected to electroless copper plating using a palladium catalyst or the like to form a seed layer 105. The seed layer serves to form a power supply layer for electrolytic copper plating, and is preferably formed to a thickness of approximately 0.1 to 2.0 μm. If the seed layer is 0.1 μm or thicker, it tends to be possible to suppress a decrease in connection reliability during electrolytic copper plating, while if it is 2.0 μm or thinner, it is not necessary to increase the etching depth when flash etching the seed layer between wirings, and damage to the wiring during etching tends to be suppressed.

[0123] The electroless copper plating process is carried out by depositing metallic copper on the surface of the via and interlayer insulating layer through a reaction between copper ions and a reducing agent. The electroless plating method and the electrolytic plating method may be known methods and are not particularly limited, but the catalyst used in the electroless plating step is preferably a palladium-tin mixed catalyst, and the primary particle size of the catalyst is preferably 10 nm or less. In addition, the plating composition used in the electroless plating step preferably contains hypophosphorous acid as a reducing agent. Commercially available electroless copper plating solutions can be used, such as "MSK-DK" manufactured by Atotech Japan Co., Ltd. and the "ThruCup (registered trademark) PEA ver. 4" series manufactured by Uemura Kogyo Co., Ltd.

[0124] After the electroless copper plating process, a dry film resist is thermocompressed onto the electroless copper plating using a roll laminator. The thickness of the dry film resist must be greater than the wiring height after electrolytic copper plating, and from this viewpoint, a dry film resist with a thickness of 5 to 30 μm is preferred. As the dry film resist, the "Photec" series manufactured by Hitachi Chemical Co., Ltd., etc., is used. After thermocompression bonding of the dry film resist, the dry film resist is exposed, for example, through a mask on which the desired wiring pattern is drawn. The exposure can be performed using the same equipment and light source as those used to form vias in the photosensitive resin film. After exposure, the support film on the dry film resist is peeled off, and development is performed using an alkaline aqueous solution to remove the unexposed portions, forming a resist pattern 106. Thereafter, if necessary, a process of removing development residues of the dry film resist using plasma or the like may be performed. After development, copper electroplating is carried out to form a copper circuit layer 107 and fill vias.

[0125] After electrolytic copper plating, the dry film resist is stripped using an alkaline aqueous solution or an amine-based stripper. After the dry film resist is stripped, the seed layer between the wirings is removed (flash etching). Flash etching is performed using an acidic solution such as sulfuric acid and hydrogen peroxide, and an oxidizing solution. Specific examples include "SAC" manufactured by JCU Corporation and "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc. After flash etching, palladium and other materials adhering to the portions between the wirings are removed as necessary. Palladium removal is preferably performed using an acidic solution such as nitric acid or hydrochloric acid.

[0126] After the dry film resist is removed or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently heat-cures any unreacted thermosetting components, thereby improving the electrical insulation reliability, curing characteristics, and adhesive strength with plated copper. The thermosetting conditions vary depending on the type of resin composition, but a curing temperature of 150 to 240°C and a curing time of 15 to 100 minutes are preferred. The post-baking treatment completes the entire process for manufacturing a printed wiring board using the photovia method, but this process is repeated to manufacture the board depending on the number of interlayer insulating layers required. A solder resist layer 108 is preferably formed as the outermost layer.

[0127] The method for manufacturing a multilayer printed wiring board in which vias are formed using the photosensitive resin composition of this embodiment has been described above, but the photosensitive resin composition of this embodiment has excellent pattern resolution, so it is also suitable for forming cavities for incorporating chips, passive elements, etc. The cavities can be suitably formed, for example, by using a drawing pattern that can form the desired cavities when forming a pattern by exposing the photosensitive resin film in the above description of the multilayer printed wiring board. Furthermore, the photosensitive resin composition of this embodiment is also useful as a surface protection film for solder resist and the like.

[0128] [Semiconductor Package] The present invention also provides a semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board of the present embodiment. The semiconductor package of the present embodiment can be manufactured by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the multilayer printed wiring board of the present invention and encapsulating the semiconductor element with an encapsulating resin or the like. [Example]

[0129] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The properties of the photosensitive resin compositions obtained in each example were evaluated by the methods shown below.

[0130] [1. Evaluation of photosensitivity characteristics (via resolution)] A 1.0 mm thick copper-clad laminate (MCL-E-67, Hitachi Chemical Co., Ltd.) was laminated using a press-type vacuum laminator (MVLP-500, Meiki Seisakusho Co., Ltd., product number) while peeling off the support film and the protective film (protective layer) of the photosensitive resin film with protective film prepared in each example, to obtain a laminate with a photosensitive layer. The lamination conditions were a pressure of 0.4 MPa, a press hot plate temperature of 75°C, a vacuum time of 40 seconds, a lamination press time of 60 seconds, and an air pressure of 4 kPa or less. Next, an i-line exposure system (UX-2240SM-XJ-01, manufactured by Ushio Inc., product number) was used to expose the vias to 100 to 500 mJ / cm through a negative mask having via patterns of predetermined sizes (opening diameter sizes: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, and 15 μmφ). 2 in the range of 50 mJ / cm 2 After that, the film was exposed to light while changing the temperature by 1.765 × 10 for a time equivalent to twice the shortest development time (the shortest time required for the unexposed portion of the photosensitive layer to be removed) at 30°C in a 1% by mass aqueous sodium carbonate solution. 5 The unexposed areas were then developed by spray development at a pressure of 2,000 mJ / cm using an ultraviolet exposure device. 2 The resulting copper-clad laminate was exposed to light at an exposure dose of 1000 ppm and heated at 170°C for 1 hour to prepare a test piece having a via pattern of a predetermined size formed from the cured product of the photosensitive resin composition on the copper-clad laminate. The formed via pattern was observed and evaluated according to the following evaluation criteria. A rating of A indicates excellent photosensitivity. A: The minimum diameter of the opening was 5 μmφ or less. C: The minimum diameter of the opening was 6 μmφ or more.

[0131] [2. Evaluation of peelability from support film] A 1.0 mm thick copper-clad laminate (MCL-E-67, Hitachi Chemical Co., Ltd.) was laminated using a press-type vacuum laminator (MVLP-500, Meiki Seisakusho Co., Ltd., product number) while peeling off the support film and the protective film (protective layer) of the photosensitive resin film prepared in each example, to obtain a laminate with a photosensitive layer. The lamination conditions were a pressure of 0.4 MPa, a press hot plate temperature of 75°C, a vacuum time of 40 seconds, a lamination press time of 20 seconds, and an air pressure of 4 kPa or less. A peel force test was conducted using a small desktop testing machine (EZ-SX, Shimadzu Corporation, product number) to peel the support film from the photosensitive layer under specified peel conditions (peel angle 180°, peel speed 0.2 m / min). The maximum stress per 25 mm width was recorded as the peel force of the protective layer and evaluated according to the following criteria. Since the higher the peel force between the support film and the photosensitive layer, the more likely defects are to occur in the image pattern formed using the photoresist, the evaluation was based on the following criteria. A: The peeling force is 0.01N / 25mm or more and 0.5N / 25mm or less. B: The peeling force is greater than 0.5 N / 25 mm and less than 1.0 N / 25 mm. C: Peel force is more than 1.0 N / 25 mm.

[0132] <Synthesis Example 1> Synthesis of acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 1 [component (A1-1)] 250 parts by mass of a dicyclopentadiene-type epoxy resin ["XD-1000" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 252 g / eq, softening point 74.2°C, corresponding to component (a1) and represented by the general formula (a1-1) above; number of ring carbon atoms in the alicyclic skeleton: 10], 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90°C, and stirred to react, until the mixture was completely dissolved. Next, the obtained solution was cooled to 60°C, 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100°C and reacted until the acid value of the solution reached 1 mgKOH / g. To the reacted solution, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to component (a3)) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80°C and reacted for 6 hours. Thereafter, the mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene-type epoxy acrylate (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group- and alicyclic skeleton-containing epoxy derivative 1") having a solid content of 73 mass %.

[0133] <Examples 1 to 6 and Comparative Examples 1 to 4> (Preparation of Photosensitive Resin Composition) Photosensitive resin compositions were prepared by blending components according to the formulations and amounts shown in Table 1 and kneading them in a three-roll mill. In each example, methyl ethyl ketone was added as needed to adjust the concentration, and photosensitive resin compositions with a solids concentration of 60% by mass were obtained. (Preparation of photosensitive resin film) A 16 μm-thick polyethylene terephthalate film (G2-16, Teijin Limited, product name) was used as a support film, and the photosensitive resin composition prepared in each example was applied to the support film so that the film thickness after drying would be 5 μm, and then dried at 75° C. for 30 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a polyethylene film (NF-15, Tamapoly Corporation, product name) was laminated as a protective film to the surface of the photosensitive resin film (photosensitive layer) opposite the side in contact with the support film, and a photosensitive resin film with the support film and protective film laminated together was produced. The photosensitive resin film thus prepared was subjected to evaluation according to the above-mentioned methods. The results are shown in Table 1.

[0134] [Table 1]

[0135] The components used in each example are as follows: (A) component; Acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 1 [component (A1-1)]: The one obtained in Synthesis Example 1 was used. Dipentaerythritol pentaacrylate [ingredient (Aiii)] (B) Ingredients; Photopolymerization initiator 1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, acetophenones Photopolymerization initiator 2: bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, acylphosphine oxides Photopolymerization initiator 3: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) (see structure below), oxime esters [ka]

[0136] (C) Component; Alicyclic skeleton-containing epoxy resin: "XD-1000", dicyclopentadiene-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., product name), epoxy equivalent 252 g / eq, softening point 74.2°C Biphenyl-type epoxy resin: "YX-4000" (product name, manufactured by Mitsubishi Chemical Corporation) Naphthalene-type epoxy resin: "HP-4710" (manufactured by DIC Corporation, product name) (F) component; Silica: "SFP-20M" (product name, manufactured by Denka Co., Ltd., average particle size 0.3 μm) (G) Ingredients; Pigment: CI Pigment Blue 15 (phthalocyanine pigment, manufactured by Sanyo Pigment Co., Ltd.) (H) Component; Hardener: Finely ground melamine (Nissan Chemical Co., Ltd., product name)

[0137] Table 1 shows that in the Examples, small vias of 5 μmφ or less were formed by batch formation of vias using photolithography, and that not only were the photosensitive properties (via resolution) excellent, but also the releasability from the support film was excellent. On the other hand, in Comparative Examples 1, 2, and 4, which did not contain component (C1), and Comparative Example 3, which contained a low amount of component (C1), the releasability from the support film was poor and the photosensitive properties (via resolution) were deteriorated. [Explanation of symbols]

[0138] 100A multilayer printed wiring board 102 Circuit Pattern 103 Interlayer insulating layer 104 Beer (Beer Hall) 105 seed layer 106 Resist Pattern 107 Copper circuit layers 108 Solder resist layer

Claims

1. A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, and (C) a thermosetting resin, the (A) photopolymerizable compound having an ethylenically unsaturated group includes (A1) a photopolymerizable compound having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, one of the raw materials of the photopolymerizable compound (A1) having an ethylenically unsaturated group is an alicyclic skeleton-containing epoxy resin (a1), the alicyclic skeleton of the (a1) alicyclic skeleton-containing epoxy resin contains a saturated dicyclopentadiene skeleton, a photosensitive resin composition, wherein the (C) thermosetting resin comprises (C1) a thermosetting resin having an alicyclic skeleton, the content of the component (C1) being 10 parts by mass or more per 100 parts by mass of the (A) component, and the composition satisfies the following condition (i) or (ii): Condition (i): The thermosetting resin (C) contains a thermosetting resin (C2) that does not have an alicyclic skeleton, and the content ratio of the component (C1) to the component (C2) [component (C1) / component (C2)] (mass ratio) is 55 / 45 to 95 / 5. Condition (ii): The (C) thermosetting resin does not include (C2) a thermosetting resin that does not have an alicyclic skeleton.

2. 2. The photosensitive resin composition according to claim 1, wherein the photopolymerizable compound (A) having an ethylenically unsaturated group further comprises at least one selected from the group consisting of (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a difunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups.

3. 3. The photosensitive resin composition according to claim 1, wherein in both the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, and the thermosetting resin (C1) having an alicyclic skeleton, the alicyclic skeleton is an alicyclic skeleton having 5 to 20 ring carbon atoms.

4. 3. The photosensitive resin composition according to claim 1, wherein in both of the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, and the thermosetting resin (C1) having an alicyclic skeleton, the alicyclic skeleton comprises two or more rings.

5. 5. The photosensitive resin composition according to claim 1, wherein in both of the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, and the thermosetting resin (C1) having an alicyclic skeleton, the alicyclic skeleton consists of three rings.

6. 6. The photosensitive resin composition according to claim 1, wherein in both the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, and the thermosetting resin (C1) having an alicyclic skeleton, the alicyclic skeleton is represented by the following general formula (a): 【Chemical 1】 (In general formula (a), R Ａ１ represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. １ is an integer from 0 to 6. * is a binding site to another structure.)

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (A1) photopolymerizable compound having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton is represented by the following general formula (A-1): 【Chemistry 2】 (In general formula (A-1), R Ａ１ represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. Ａ２ represents an alkyl group having 1 to 12 carbon atoms. Ａ３ is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least one R Ａ３ is an organic group having an ethylenically unsaturated group and an acidic substituent. Ａ１ is an integer from 0 to 6, m Ａ２ is an integer from 0 to 3. Ａ１ is between 0 and 10.)

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein in the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, the acidic substituent is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group.

9. The photosensitive resin composition according to any one of claims 1 to 8, wherein the thermosetting resin having an alicyclic skeleton (C1) is represented by the following general formula (C-1): 【Chemistry 3】 (In general formula (C-1), R Ｃ１ represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. Ｃ２ represents an alkyl group having 1 to 12 carbon atoms. Ｃ１ is an integer from 0 to 6, m Ｃ２ is an integer from 0 to 3. Ｃ１ is between 0 and 10.)

10. The photosensitive resin composition according to any one of claims 1 to 9, wherein the component (C2) is a bisphenol-based epoxy resin, a naphthol-type epoxy resin, a naphthalene-type epoxy resin, a biphenyl-type epoxy resin, or a naphthylene ether-type epoxy resin.

11. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (F) an inorganic filler.

12. The photosensitive resin composition according to any one of claims 1 to 11, further comprising (G) a curing agent.

13. A photosensitive resin composition for forming a photovia, comprising the photosensitive resin composition according to any one of claims 1 to 12.

14. A photosensitive resin composition for an interlayer insulating layer, comprising the photosensitive resin composition according to any one of claims 1 to 12.

15. A photosensitive resin film comprising the photosensitive resin composition according to any one of claims 1 to 12.

16. A photosensitive resin film for an interlayer insulating layer, comprising the photosensitive resin composition according to any one of claims 1 to 12.

17. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of claims 1 to 12.

18. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to claim 15.

19. A semiconductor package comprising the multilayer printed wiring board according to claim 17 or 18 mounted with a semiconductor element.

20. A method for producing a multilayer printed wiring board, comprising the following steps (1) to (4): Step (1): A step of laminating the photosensitive resin film according to claim 15 onto one or both surfaces of a circuit board. Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1). Step (3): A step of roughening the via and the interlayer insulating layer. Step (4): forming a circuit pattern on the interlayer insulating layer.

Images