Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board and semiconductor package, and manufacturing method of 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, which are excellent in resolution of via, adhesion strength to plated copper, crack resistance, and electric insulation reliability; furthermore, to provide a photosensitive resin film and a photosensitive resin film for an interlayer insulation layer, which are each composed of the photosensitive resin composition; furthermore, to provide a multilayer printed wiring board and a semiconductor package; and to provide a manufacturing method of the multilayer printed wiring board.SOLUTION: A photosensitive resin composition for a multilayer printed wiring board contains: (A) a photopolymerizable compound having an ethylenically unsaturated group; (B) a photopolymerization initiator; (C) a thermosetting resin; and (F) an inorganic filler. Therein (A) the photopolymerizable compound having the ethylenically unsaturated group contains (A1) a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group, the component (A1) is represented by general formula (A-1) described in the specification, and (C) the thermosetting resin contains a biphenyl 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 manufacturing a multilayer printed wiring board.

Background Art

[0002] In recent years, miniaturization and high performance of electronic devices have advanced, and in multilayer printed wiring boards, an increase in the number of circuit layers and high density due to miniaturization of wiring have been progressing. In particular, the high density of semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) on which semiconductor chips are mounted is remarkable, and in addition to miniaturization of wiring, thinning of the insulating film and further reduction in the diameter of vias (also referred to as "via holes") for interlayer connection are required. In addition, with the thinning of the insulating film in the printed wiring board, excellent electrical insulation reliability between layers [particularly, electrical insulation reliability after moisture absorption (HAST (High Accelerated Stress Test) resistance)] is also required.

[0003] As a method for manufacturing a printed wiring board, there is a method for manufacturing a multilayer printed wiring board by a build-up method in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated (see, for example, Patent Document 1). In multilayer printed wiring boards, with the miniaturization of circuits, a semi-additive process in which circuits are formed by plating has become mainstream. In the conventional semi-additive process, for example, (1) a thermosetting resin film is laminated on 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 desmear treatment and roughening treatment are performed by alkaline permanganate treatment or the like. (3) Thereafter, electroless copper plating treatment is performed on the substrate, and after pattern formation using a resist, electrolytic copper plating is performed to form a copper circuit layer. (4) Next, the resist is peeled off, and flash etching of the electroless layer is performed to form the copper circuit.

[0004] As described above, laser processing is the mainstream method for forming vias in an interlayer insulating layer formed by curing a thermosetting resin film. However, the reduction in the diameter of vias by laser irradiation using a laser processing machine has reached its limit. Furthermore, in the formation of vias by a laser processing machine, it is necessary to form each via hole one by one. When it is necessary to provide a large number of vias due to high density, it takes a great deal of time to form the vias, resulting in a problem of poor manufacturing efficiency.

[0005] Under such circumstances, as a method capable of forming a large number of vias at once, 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, and having a content of the (D) inorganic filler of 10 to 80% by mass is used, and a method for forming a plurality of small-diameter vias at once by a photolithography method has been proposed (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] In Patent Document 2, one of the problems is to suppress the decrease in the adhesive strength with electroless copper due to using a photosensitive resin composition instead of a conventional thermosetting resin composition as the material for the interlayer insulating layer or the surface protective layer. Further, the resolution of vias, the adhesion to substrates and chip components made of silicon materials are also problems, and it is stated that these have been solved. However, in addition to further miniaturization of wiring, the thinning of the insulating film and the reduction in the diameter of via holes for interlayer connection are progressing. Therefore, the requirements for improvement in the adhesive strength with electroless copper and the electrical insulation reliability are increasing. Therefore, there is still room for further improvement in the photosensitive resin composition of Patent Document 2 in terms of the adhesive strength with electroless copper and the electrical insulation reliability. Similarly, as the material for the interlayer insulating layer, it is also conceivable to divert a photosensitive resin composition or the like, which is a material for a conventional solder resist. However, since the interlayer insulating layer requires characteristics that are not necessary for the solder resist (for example, electrical insulation reliability between layers, adhesive strength with electroless copper, high heat resistance that can withstand multiple heatings, high dimensional accuracy of via shapes, etc.), it is difficult to predict whether it can withstand practical use as an interlayer insulating layer, and it cannot be easily diverted. Also, it was difficult to say that conventional photosensitive resin compositions had sufficient crack resistance to withstand reflow mounting.

[0008] 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 interlayer insulating layers that are excellent in via resolution, adhesive strength with electroless copper, crack resistance, and electrical insulation reliability. Further, to provide a photosensitive resin film and a photosensitive resin film for interlayer insulating layers composed of the photosensitive resin composition, to provide a multilayer printed wiring board and a semiconductor package, and to provide a method for manufacturing the multilayer printed wiring board.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive resin composition containing the following components (A) and (B) can solve the above problems, wherein the component (A) contains a "photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group". That is, the present invention relates to the following [1] to

[20] .

[0010] [1] A photosensitive resin composition containing a photopolymerizable compound having an ethylenically unsaturated group (A) and a photopolymerization initiator (B), wherein the photopolymerizable compound having an ethylenically unsaturated group (A) includes a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group (A1). [2] The photosensitive resin composition according to [1] above, wherein the photopolymerizable compound having an ethylenically unsaturated group (A) further includes at least one selected from the group consisting of a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group (Ai), a bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups (Aii), and a polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups (Aiii). [3] The photosensitive resin composition according to [1] or [2] above, wherein in the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group (A1), the alicyclic skeleton is an alicyclic skeleton having 5 to 20 ring-forming carbon atoms. [4] The photosensitive resin composition according to [1] or [2] above, wherein in the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group (A1), the alicyclic skeleton consists of two or more rings. [5] The photosensitive resin composition according to [1], [2] or [4] above, wherein in the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group (A1), the alicyclic skeleton consists of three rings. [6] The photosensitive resin composition according to any one of [1] to [5] above, wherein in the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group (A1), the alicyclic skeleton is represented by the following general formula (a). [Chemical formula] (In general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic skeleton. m 1 is an integer from 0 to 6. * is a bonding site to another structure.) [7] The photosensitive resin composition according to any one of [1] to [6] above, wherein the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the (A1) ethylenically unsaturated group is represented by the following general formula (A-1). [Chemical formula] (In general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic skeleton. R A2 represents an alkyl group having 1 to 12 carbon atoms. R 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. m 1 is an integer from 0 to 6, m 2 is an integer from 0 to 3. n is from 0 to 10.) [8] In the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the (A1) ethylenically unsaturated group, 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. The photosensitive resin composition according to any one of [1] to [7] above. [9] The photosensitive resin composition according to any one of [1] to [8] above, further containing (C) a thermosetting resin.

[10] The photosensitive resin composition according to any one of [1] to [9] above, further containing (D) an elastomer.

[11] The photosensitive resin composition according to

[10] above, wherein the (D) elastomer contains at least one selected from the group consisting of styrenic elastomers, olefinic elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, acrylic elastomers, and silicone elastomers.

[12] The photosensitive resin composition according to any one of [1] to

[11] above, further containing an (F) inorganic filler.

[13] A photosensitive resin composition for forming a photvia, comprising the photosensitive resin composition according to any one of [1] to

[12] above.

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

[12] above.

[15] A photosensitive resin film, comprising the photosensitive resin composition according to any one of [1] to

[12] above.

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

[12] above.

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

[12] above.

[18] A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to

[15] above.

[19] A semiconductor package having a semiconductor element mounted on the multilayer printed wiring board according to

[17] or

[18] above.

[20] A method for manufacturing a multilayer printed wiring board, comprising the following steps (1) to (4). Step (1): A step of laminating the photosensitive resin film according to

[15] above on 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 the step (1). Step (3): A step of roughening the vias and the interlayer insulating layer. Step (4): A step of forming a circuit pattern on the interlayer insulating layer.

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a photosensitive resin composition, a photosensitive resin composition for forming a photo via, and a photosensitive resin composition for an interlayer insulating layer, which are excellent in via resolution, adhesion strength to plated copper, crack resistance, and electrical insulation reliability. Further, it is possible to provide a photosensitive resin film composed of the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer, and a multilayer printed wiring board and a semiconductor package containing 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, high adhesion strength between the interlayer insulating layer and the plated copper, and excellent electrical insulation reliability. The vias of the multilayer printed wiring board obtained by the manufacturing method of the present invention can be vias having a smaller diameter than the vias formed by laser processing.

Brief Description of the Drawings

[0012]

Figure 1

Modes for Carrying Out the Invention

[0013] In the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value or the upper limit value of other numerical ranges, respectively. Furthermore, in this specification, the content rate of each component in the photosensitive resin composition means the total content rate of the plurality of substances present in the photosensitive resin composition when there are a plurality of substances corresponding to each component, unless otherwise specified. In this specification, the "number of ring-forming carbon atoms" is the number of carbon atoms necessary to form a ring, and does not include the number of carbon atoms of substituents that the ring has. For example, both the cyclohexane skeleton and the methylcyclohexane skeleton have 6 ring-forming carbon atoms. In addition, aspects in which the matters described in this specification are arbitrarily combined are also included in the present invention.

[0014] [Photosensitive resin composition, photosensitive resin composition for forming photovias, and photosensitive resin composition for interlayer insulating layer] The photosensitive resin composition according to one embodiment of the present invention (hereinafter sometimes simply referred to as this embodiment) is a photosensitive resin composition containing (A) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group contains (A1) a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the ethylenically unsaturated group. In this specification, the above components may be referred to as component (A), component (B), component (A1), etc., respectively, and other components may also be abbreviated in the same way. In this specification, the "resin component" refers to the above component (A), component (B), etc., and other components that may be contained as necessary (for example, components (C), (D), (E), and (H), etc.) are also included, but the (F) inorganic filler and (G) pigment that may be contained as necessary and will be described later are not included. Further, the "solid content" refers to the non-volatile components excluding volatile substances such as water and solvents contained in the photosensitive resin composition, and indicates the components that remain without volatilization when the resin composition is dried, and also includes those in a liquid state, a treacle state, and a wax state at room temperature around 25°C.

[0015] Since the photosensitive resin composition of this embodiment is suitable for via formation by photolithography (also referred to as photovia formation), the present invention also provides a photosensitive resin composition for forming photovias. Further, since the photosensitive resin composition of this embodiment is excellent in via resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability, and is useful as an interlayer insulating layer of a multilayer printed wiring board, the present invention also provides a photosensitive resin composition for an interlayer insulating layer. In this specification, when referring to a photosensitive resin composition, it also includes a photosensitive resin composition for forming photovias and a photosensitive resin composition for an interlayer insulating layer. Note that the photosensitive resin composition of this embodiment is useful as a negative photosensitive resin composition. Hereinafter, each component that the photosensitive resin composition may contain will be described in detail.

[0016] <(A) Photopolymerizable compound having an ethylenically unsaturated group> The photosensitive resin composition of the present embodiment contains, as component (A), a photopolymerizable compound having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group of 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. As the ethylenically unsaturated group, a (meth)acryloyl group is preferable. In the present invention, component (A) includes a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the ethylenically unsaturated group described later. By component (A) containing component (A1), a photosensitive resin composition excellent in via resolution, adhesion strength to electroless copper, crack resistance, and electrical insulation reliability can be obtained. Hereinafter, component (A1) will be described in detail.

[0017] ((A1) Photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group) Examples of the ethylenically unsaturated group of component (A1) include the same ones as the ethylenically unsaturated groups described above, and 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 is preferable, a vinyl group, an allyl group, and a (meth)acryloyl group are more preferable, and a (meth)acryloyl group is even more preferable. Examples of the acidic substituent of component (A1) include at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is more preferable.

[0018] As the alicyclic skeleton of the (A1) component, from the viewpoints of via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, an alicyclic skeleton having 5 to 20 carbon atoms in the ring formation is preferable, an alicyclic skeleton having 5 to 18 carbon atoms in the ring formation is more preferable, an alicyclic skeleton having 6 to 18 carbon atoms in the ring formation is further preferable, an alicyclic skeleton having 8 to 14 carbon atoms in the ring formation is particularly preferable, and an alicyclic skeleton having 8 to 12 carbon atoms in the ring formation is most preferable. Also, from the viewpoints of via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, the alicyclic skeleton preferably consists of two or more rings, more preferably consists of 2 to 4 rings, and further preferably consists of 3 rings. Examples of the alicyclic skeleton of two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, a saturated dicyclopentadiene skeleton, and the like. As the alicyclic skeleton, from the viewpoints of via resolution, adhesion strength with plated copper, crack resistance, and electrical insulation reliability, a saturated dicyclopentadiene skeleton is preferable, and an alicyclic skeleton (saturated dicyclopentadiene skeleton) represented by the following general formula (a) is more preferable. [Chemical formula] (In general formula (a), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any position in the above alicyclic skeleton. m 1 is an integer of 0 to 6. * is a bonding site to another structure.)

[0019] In general formula (a), examples of the alkyl group having 1 to 12 carbon atoms represented by R A1 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, and the like. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable. m 1 is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0. m 1 When it is an integer of 2 to 6, a plurality of R A1They may be the same or different from each other. Further, a plurality of Rs A1 may be substituted on the same carbon atom as much as possible, or may be substituted on different carbon atoms. * is a bonding site to another structure and may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to the carbon atom represented by 1 or 2 in the following general formula (a') and the carbon atom represented by any one of 3 to 4. [Chemical formula] (In the general formula (a'), R A1 , m 1 and * are the same as those in the general formula (a).)

[0020] As the component (A1), from the viewpoints of being alkali-developable and having excellent via resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability, a compound obtained by modifying (a1) an alicyclic skeleton-containing epoxy resin with (a2) an ethylenically unsaturated group-containing organic acid [hereinafter sometimes referred to as the component (A')] is reacted with (a3) a saturated group- or unsaturated group-containing polybasic acid anhydride, and the "epoxy derivative containing an acid-modified ethylenically unsaturated group and an alicyclic skeleton" is preferable.

[0021] -(a1) Alicyclic skeleton-containing epoxy resin- The above (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 preferable.

[0022] In the present invention, as the epoxy resin, at least an epoxy resin having an alicyclic skeleton is used. The alicyclic skeleton is described in the same manner as the alicyclic skeleton of the component (A1) described above, and the preferred embodiments are also the same. (a1) As the alicyclic skeleton-containing epoxy resin, an epoxy resin represented by the following general formula (a1-1) is preferable. Also, an epoxy resin having a structural unit represented by the following general formula (a1-2) is preferable.

Chemical formula

Chemical formula

[0023] In general formulas (a1-1) and (a1-2), R A1 is the same as R A1 in general formula (a), and the preferred embodiments are also the same. As the alkyl group having 1 to 12 carbon atoms represented by R A2 in general formula (a1-1), for example, 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. can be mentioned. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. m 1 in general formulas (a1-1) and (a1-2) is the same as m 1 in general formula (a), and the preferred embodiments are also the same. m 2 in general formula (a1-1) is an integer from 0 to 3, 0 or 1 is preferable, and 0 is more preferable. In the general formula (a1-1), n represents the number of repetitions of the structural unit within the parentheses and is from 0 to 10. Usually, since the epoxy resin is a mixture of those having different numbers of repetitions of the structural unit within the parentheses, in that case, n is represented by the average value of the mixture. As n, 2 to 10 is preferable.

[0024] (a1) As the alicyclic skeleton-containing epoxy resin, commercially available products may be used. Examples of commercially available products include XD-1000 (manufactured by Nippon Kayaku Co., Ltd., trade name), EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200HH, EPICLON HP-7200HHH (manufactured by DIC Corporation, trade name, "EPICLON" is a registered trademark), and the like.

[0025] (a1) As the epoxy resin, an epoxy resin other than the epoxy resin having the 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 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 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 resin; biphenyl aralkyl type epoxy resin; stilbene type epoxy resin; naphthalene type epoxy resin, naphthol novolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthylene ether type epoxy resin, and other naphthalene skeleton-containing type epoxy resins; biphenyl type epoxy resin; xylylene type epoxy resin; dihydroanthracene type epoxy resin; aliphatic chain type epoxy resin; rubber-modified epoxy resin, and the like.

[0026] -(a2) Ethylenically unsaturated group-containing organic acid - The (a2) ethylenically unsaturated group-containing organic acid is not particularly limited, but an ethylenically unsaturated group-containing monocarboxylic acid is preferred. The ethylenically unsaturated group is as described for the ethylenically unsaturated group in the component (A1). Examples of the ethylenically unsaturated group-containing monocarboxylic acid include acrylic acid; acrylic acid derivatives such as a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid; a half-ester compound that is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride; a half-ester compound that is a reaction product of an ethylenically unsaturated group-containing monoglycidyl ether or an ethylenically unsaturated group-containing monoglycidyl ester and a dibasic acid anhydride; and the like. Among these, acrylic acid is preferred. The component (a2) may be used alone or in combination of two or more.

[0027] 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.

[0028] 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 half-ester compound, which is an example of the 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, glycidyl methacrylate and the like.

[0029] As the dibasic acid anhydride used for the synthesis of the semi-ester compound, those containing a saturated group or those containing an unsaturated group may be used. 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, itaconic anhydride, and the like.

[0030] Although not particularly limited, in the reaction between the component (a1) and the component (a2), it is preferable to react the component (a2) at a ratio of 0.6 to 1.05 equivalents with respect to 1 equivalent of the epoxy group of the component (a1), and it may also be reacted at a ratio of 0.8 to 1.0 equivalents. By reacting at such a ratio, the photopolymerizability is improved, that is, the photosensitivity becomes large, and the resolution of the via tends to be improved.

[0031] The component (a1) and the component (a2) can be dissolved in an organic solvent and reacted. 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, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

[0032] 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; phosphine catalysts such as triphenylphosphine, etc. Among these, phosphine catalysts are preferable, and triphenylphosphine is more preferable. The usage amount of the catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass in total of the component (a1) and the component (a2). With the above usage amount, the reaction between the component (a1) and the component (a2) tends to be promoted.

[0033] Also, for the purpose of preventing polymerization during the reaction, it is preferable to use a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc. When using a polymerization inhibitor, from the viewpoint of improving the storage stability of the composition, its usage amount is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 part by mass, and still more preferably 0.05 to 0.5 part by mass with respect to 100 parts by mass in total of the component (a1) and the component (a2).

[0034] From the viewpoint of productivity, the reaction temperature between the component (a1) and the component (a2) is preferably 60 to 150 °C, more preferably 70 to 120 °C, and still more preferably 80 to 110 °C.

[0035] Thus, it is presumed that the component (A') formed by reacting the component (a1) and 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).

[0036] -(a3) Polybasic acid anhydride- As the (a3) component, it may contain a saturated group or an unsaturated group. Examples of the (a3) component include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, etc. Among these, from the viewpoint of the resolution of the via, tetrahydrophthalic anhydride is preferable.

[0037] By further reacting the obtained (A’) component with an (a3) component containing a saturated or unsaturated group, it is presumed that the hydroxyl group of the (A’) component (including the hydroxyl group originally present in the (a1) component) and the acid anhydride group of the (a3) component are semi-esterified to form an (A1-1) acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative.

[0038] In the reaction between the (A’) component and the (a3) component, for example, by reacting 0.1 to 1.0 equivalents of the (a3) component with respect to 1 equivalent of the hydroxyl group in the (A’) component, the acid value of the (A1-1) acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative can be adjusted. The acid value of the (A1-1) acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative is preferably 20 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g, and even more preferably 40 to 100 mgKOH / g. If the acid value is 20 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution tends to be excellent, and if it is 150 mgKOH / g or less, the electrical properties of the cured film tend to improve.

[0039] From the viewpoint of productivity, the reaction temperature between the (A’) component and the (a3) component is preferably 50 to 150 °C, more preferably 60 to 120 °C, and even more preferably 70 to 100 °C.

[0040] As described above, the photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the (A1) ethylenically unsaturated group is not particularly limited, but is preferably represented by the following general formula (A-1). [Chemical formula] (In the general formula (A-1), R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic skeleton. R A2 represents an alkyl group having 1 to 12 carbon atoms. R 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. m 1 is an integer of 0 to 6, m 2 is an integer of 0 to 3. n is 0 to 10.)

[0041] R A1 , R A2 , m 1 , m 2 and n in the general formula (a1-1) are the same as those in the general formula (a1-1), and the preferred ones are also the same. R A3 is as defined above, but the glycidyl group in the general formula (a1-1) corresponds to the site formed by reacting with the (a2) component and the (a3) component, and a definition is made in consideration of the fact that some of the glycidyl groups remain unreacted. That is, the "organic group having an ethylenically unsaturated group" which is an option of R A3 is a group derived from the (a2), 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), then R A3It becomes an "organic group having an ethylenically unsaturated group and an acidic substituent", but the site that reacts only with the component (a2) becomes an "organic group having an ethylenically unsaturated group", and the site that does not react with either the component (a2) or (a3) becomes a "glycidyl group".

[0042] ((A1) Molecular weight of a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with an ethylenically unsaturated group) The weight average molecular weight (Mw) of the 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, the adhesive strength, heat resistance, and electrical insulation reliability with electrodeposited copper are improved. In particular, it is preferable that the weight average molecular weight (Mw) of the (A1-1) acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative is within the above range. Here, in this specification, 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, it is a value measured according to the method described below. <Method for measuring weight average molecular weight> The weight average molecular weight was measured with the following GPC measuring device and measuring conditions, and the value converted using the calibration curve of standard polystyrene was taken as the weight average molecular weight. Also, for the preparation of the calibration curve, 5 sample sets ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation) were used as standard polystyrenes. (GPC measuring device) GPC device: High-speed GPC device "HCL-8320GPC", detector is a differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measuring conditions) Solvent: Tetrahydrofuran (THF) Measuring temperature: 40 °C Flow rate: 0.35 mL / min Sample concentration: 10 mg / THF 5 mL Injection volume: 20 μL

[0043] ((A2-1) Acid-modified ethylene unsaturated group-containing epoxy derivative without alicyclic skeleton) As the photopolymerizable compound having an ethylenically unsaturated group, further, a compound obtained by modifying (a21) an epoxy resin (however, not containing an alicyclic skeleton) with (a22) an ethylenically unsaturated group-containing organic acid and reacting with (a23) a saturated group or unsaturated group-containing polybasic acid anhydride, an embodiment including “(A2-1) acid-modified ethylene unsaturated group-containing epoxy derivative without alicyclic skeleton” may also be used.

[0044] The (a21) epoxy resin is not particularly limited as long as it is an epoxy resin without an alicyclic skeleton, and examples include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and the like. Among these, glycidyl ether type epoxy resins are preferred. In addition, the (a21) epoxy resin is classified into various epoxy resins depending on the difference in the main skeleton, and in each of the above types of epoxy resins, it is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; novolak type epoxy resins other than the above bisphenol-based novolak type epoxy resins, such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and biphenyl novolak type epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolak 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 chain epoxy resin; rubber-modified epoxy resin, etc. Among these, bisphenol-based novolak type epoxy resins are preferred, and bisphenol F novolak type epoxy resin is more preferred.

[0045] The (a22) ethylenically unsaturated group-containing organic acid and the (a23) saturated group or unsaturated group-containing polybasic acid anhydride are described in the same manner as the description of the (a2) ethylenically unsaturated group-containing organic acid and the (a3) saturated group or unsaturated group-containing polybasic acid anhydride, and the preferred embodiments are also the same. In addition, as a method of reacting the (a23) component with the compound obtained by modifying the (a21) component with the (a22) component, reference can be made to the method of reacting the (a3) component with the compound obtained by modifying the (a1) component with the (a2) component.

[0046] (A2-1) As the acid-modified ethylenically unsaturated group-containing epoxy derivative not containing an alicyclic skeleton, commercially available products may be used. 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 (above, manufactured by Nippon Kayaku Co., Ltd., trade name), UE-9000, UE-EXP-2810PM, UE-EXP-3045 (above, manufactured by DIC Corporation, trade name), and the like.

[0047] When the component (A) contains both the component (A1-1) and the component (A2-1), from the viewpoint of the balance of properties such as via resolution, adhesion strength to plated copper, crack resistance, and electrical insulation reliability, the content ratio [(A1-1) / (A2-1)] of the component (A1-1) and the component (A2-1) is preferably 20 / 80 to 99 / 1, more preferably 50 / 50 to 99 / 1, still more preferably 60 / 40 to 99 / 1, particularly preferably 60 / 40 to 85 / 15, and most preferably 65 / 35 to 80 / 20 in terms of mass ratio.

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

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

[0050] ((A) component other than the above) As the photopolymerizable compound having an ethylenically unsaturated group (A), from the viewpoint of enhancing the chemical resistance after curing (exposure) and increasing the difference in developability resistance between the exposed portion and the unexposed portion, as the photopolymerizable compound having an ethylenically unsaturated group (A), further, (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. An embodiment containing at least one selected from the group consisting of is preferable, and an embodiment containing the (Aiii) component is more preferable. As the (Ai) to (Aiii) components, those having a molecular weight of 1,000 or less are preferable. However, in the present invention, the (Ai) to (Aiii) components do not include the (A1) component.

[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 ester 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 hydroxyethyl ester. The (Ai) component may be used alone or in combination of two or more.

[0052] ((Aii) Difunctional 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, and the like. Component (Aii) may be used alone or in combination of two or more.

[0053] ((Aiii) Polyfunctional 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 enhancing the chemical resistance after curing (exposure) and increasing the difference in developer resistance between the exposed part and the unexposed part, (meth)acrylate compounds having a skeleton derived from dipentaerythritol are preferable, and dipentaerythritol penta(meth)acrylate is more preferable. 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 a compound name) means an esterified product of XXX and (meth)acrylic acid, and the esterified product includes compounds modified with an alkyleneoxy group.

[0054] (Content of component (A)) (A) The content of component (A) is not particularly limited, but from the viewpoints of heat resistance, electrical properties, and chemical resistance, based on the total solid content of the photosensitive resin composition, it is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, still more preferably 20 to 50% by mass, particularly preferably 25 to 50% by mass, and most preferably 30 to 45% by mass.

[0055] (A) As component (A), there is no particular limitation, but from the viewpoint of photosensitive characteristics, it is preferable to use the above-mentioned component (A1) and component (Aiii) in combination. In this case, the content ratio [(A1) / (Aiii)] (mass ratio) of component (A1) and component (Aiii) is preferably 2 to 20, more preferably 2 to 15, still more preferably 2.5 to 10, and particularly preferably 3 to 8. Also, the content ratio of component (A1) to the total amount of component (A) is preferably 20 to 95% by mass, more preferably 40 to 90% by mass, still more preferably 55 to 90% by mass, and particularly preferably 70 to 90% by mass from the viewpoints of via resolution, adhesion strength to plated copper, crack resistance, and electrical insulation reliability.

[0056] <(B) Photoinitiator> As component (B) used in this embodiment, there is no particular limitation as long as it can polymerize component (A), and it can be appropriately selected from commonly used photoinitiators. Examples of component (B) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenones such as 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)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; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 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; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; oxime esters 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-acetoxyoxime), and 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]. Among these, acetophenones and thioxanthones are preferred, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone are more preferred. Acetophenones have the advantage of being less volatile and less likely to generate as outgas, and thioxanthones have the advantage of being able to undergo photocuring even in the visible light region. (Component (B) may be used alone or in combination of two or more. When two or more are used in combination, it is preferable to use acetophenones and thioxanthones in combination, and it is more preferable to use 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone in combination.)

[0057] (Content of component (B)) (The content of component (B) is not particularly limited, but based on the total solid content of the photosensitive resin composition, it is preferably 0.1 to 15% by mass, more preferably 0.15 to 5% by mass, still more preferably 0.2 to 1.5% by mass, and particularly preferably 0.2 to 0.8% by mass. If the content of component (B) is 0.1% by mass or more, there is a tendency to reduce the possibility that the exposed site elutes during development in the interlayer insulating layer formed using the photosensitive resin composition, and if it is 15% by mass or less, there is a tendency for the heat resistance to improve.)

[0058] <(B') Photoinitiator assistant> The photosensitive resin composition of this embodiment may contain a (B') photoinitiator assistant together with the above-mentioned component (B). Examples of the (B') photoinitiator assistant include tertiary amines such as ethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate, pentyl 4-dimethylaminobenzoate, triethylamine, and triethanolamine. Component (B') may be used alone or in combination of two or more.) When the photosensitive resin composition of this embodiment contains component (B'), its content is preferably 0.01 to 20% by mass, more preferably 0.2 to 5% by mass, still more preferably 0.3 to 2% by mass, based on the total amount of the resin components of the photosensitive resin composition. Note that the photosensitive resin composition of this embodiment may not contain this (B') component.)

[0059] <(C) Thermosetting resin> The photosensitive resin composition of this embodiment may further contain a thermosetting resin as component (C), and it is preferably contained. Component (C) does not include those corresponding to component (A), and in this regard, it can be said that component (C) does not have an ethylenically unsaturated group. Also, a substance having an epoxy group while satisfying the said conditions is included in component (C). When the photosensitive resin composition of this embodiment contains (C) thermosetting resin, in addition to the improvement in the adhesive strength to electrodeposited copper and insulation reliability, the heat resistance tends to be improved. Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc. Also, it is not particularly limited to these, and known thermosetting resins can be used. Among these, epoxy resin is preferred. Component (C) may be used alone or in combination of two or more.

[0060] 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.

[0061] In addition, epoxy resins are classified into various types according to the difference in 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 resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolak type epoxy resins such as bisphenol A novolak type epoxy resin and bisphenol F novolak type epoxy resin; novolak type epoxy resins other than the above bisphenol-based novolak type epoxy resins, such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, and biphenyl novolak type epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthalene type epoxy resin, naphthol novolak 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; dicyclopentadiene type epoxy resin; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; aliphatic chain epoxy resin; rubber-modified epoxy resin; and the like. Component (C) may be used alone or in combination of two or more.

[0062] Among these, in particular, from the viewpoints of heat resistance, electrical insulation reliability, and adhesion strength to electrodeposited copper, bisphenol-based epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, and cresol novolak type epoxy resins are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and biphenyl type epoxy resins are more preferred, bisphenol F type epoxy resin and biphenyl type epoxy resins are further preferred, and biphenyl type epoxy resin is particularly preferred. These can also use commercially available products. For example, bisphenol A type epoxy resins (such as "jER828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resins (such as "jER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation), naphthalene type epoxy resins (such as "HP4032D" and "HP4710" manufactured by DIC Corporation), naphthalene skeleton-containing polyfunctional epoxy resins (such as "NC7000" manufactured by Nippon Kayaku Co., Ltd.), naphthol type epoxy resins (such as "ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.), epoxy resins having a biphenyl structure (such as "NC3000H" and "NC3500" manufactured by Nippon Kayaku Co., Ltd., "YX4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation), anthracene type epoxy resins (such as "YX8800" manufactured by Mitsubishi Chemical Corporation), glycerol type epoxy resins (such as "ZX1542" manufactured by Nippon Steel Chemical & Material Co., Ltd.), naphthylene ether type epoxy resins (such as "EXA7311-G4" manufactured by DIC Corporation), cresol novolak type epoxy resins (such as "EPICLON N-680" manufactured by DIC Corporation), etc. can be mentioned.

[0063] As the epoxy resin, in addition to the above examples, epoxy-modified polybutadiene can be used. In particular, from the viewpoint of handling properties during the production of printed wiring boards, it is preferable to use a combination of an aromatic epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature as the component (C). From this viewpoint, a mode of using the above-exemplified epoxy resin (aromatic epoxy resin that is solid at room temperature) and epoxy-modified polybutadiene (epoxy resin that is liquid at room temperature) in combination is preferable. In this case, the content ratio of the two used in combination (aromatic epoxy resin that is solid at room temperature / epoxy resin that is liquid at room temperature) is preferably 95 / 5 to 60 / 40, more preferably 95 / 5 to 70 / 30, and even more preferably 90 / 10 to 75 / 25 by mass ratio.

[0064] The epoxy-modified polybutadiene preferably has a hydroxyl group at the molecular terminal, more preferably has hydroxyl groups at both molecular terminals, and even more preferably has hydroxyl groups only at both molecular terminals. Further, the number of hydroxyl groups of the epoxy-modified polybutadiene is not particularly limited as long as it is 1 or more, but is preferably 1 to 5, more preferably 1 or 2, and even more preferably 2. From the viewpoints of the adhesion strength to plated copper, heat resistance, coefficient of thermal expansion, and flexibility, the epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (C-1).

[0065] [Chemical formula] (In the above formula (C-1), a, b, and c each represent the ratio of the structural units in the parentheses, a is 0.05 to 0.40, b is 0.02 to 0.30, 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 angle brackets and is an integer of 10 to 250.)

[0066] In the general formula (C-1), the bonding order of each structural unit in the angle brackets is arbitrary. That is, the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right may be in an alternating order. When each is represented by (a), (b), and (c), -[(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)-]-, etc., there can be various bonding orders. From the viewpoints of the adhesion strength to plated copper, heat resistance, coefficient of thermal expansion, 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. Also, from the same viewpoints, y is preferably an integer of 30 to 180.

[0067] In the general formula (C-1), commercially available epoxy polybutadienes where a = 0.20, b = 0.20, c = 0.60, and y is an integer from 10 to 250 include "Epolead (registered trademark) PB3600" (manufactured by Daicel Corporation), etc.

[0068] (Content of component (C)) When the photosensitive resin composition of this embodiment contains component (C), its content is not particularly limited, but based on the total solid content of the photosensitive resin composition, it is preferably 5 to 70% by mass, more preferably 5 to 40% by mass, still more preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass. If the content of component (C) is 5% by mass or more, sufficient cross-linking of the photosensitive resin composition can be obtained, and the adhesion strength to electroless copper and the electrical insulation reliability tend to improve. On the other hand, if it is 70% by mass or less, the resolution of vias tends to be good.

[0069] <(D) Elastomer> The photosensitive resin composition of this embodiment may contain an elastomer as component (D), and it is preferably contained. By containing component (D), it tends to become a photosensitive resin composition excellent in via resolution, adhesion strength to electroless copper, and electrical insulation reliability. Also, component (D) has the effect of suppressing the decrease in flexibility and adhesion strength to electroless copper caused by the internal strain (internal stress) in the cured product due to the curing shrinkage of component (A). As component (D), an elastomer that is liquid at 25°C is preferred. Component (D) may be used alone or in combination of two or more.

[0070] Examples of the elastomer include styrenic elastomers, olefinic elastomers, polyester elastomers, urethane elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers, etc., 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 tends to contribute to heat resistance and strength, and the latter tends to contribute to flexibility and toughness. As the component (D), among the above examples, from the viewpoints of compatibility, solubility, and adhesion strength to electrodeposited copper, it is preferable to include at least one selected from the group consisting of olefinic elastomers, polyester elastomers, and urethane elastomers, and it is more preferable to include a polyester elastomer. Further, it is more preferable that the component (D) is at least one selected from the group consisting of olefinic elastomers, polyester elastomers, and urethane elastomers, and it is particularly preferable that the component (D) is a polyester elastomer.

[0071] (Styrenic elastomer) Examples of the styrenic 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. The styrenic elastomer may be used alone or in combination of two or more. Examples of the components constituting the styrenic elastomer include styrene; styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, etc. As the styrenic elastomer, those having a number average molecular weight of 1,000 to 50,000 are preferable, and those having a number average molecular weight of 3,000 to 20,000 are more preferable. In this specification, the number average molecular weight is a value determined by gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent and converted to standard polystyrene.

[0072] Styrene-based elastomers can also be commercially available products. Examples of commercially available products include Toughprene, Solprene T, Asaprene T, Toughtech (all manufactured by Asahi Kasei Corporation, "Toughprene", "Asaprene" and "Toughtech" are registered trademarks), Elastomer AR (manufactured by Aron Kasei Co., Ltd.), Clayton G, Hyperflex (all manufactured by Shell Japan Limited), JSR-TR, TSR-SIS, Dynaron (all manufactured by JSR Corporation), Denka STR (manufactured by Denka Co., Ltd.), Quintac (manufactured by Nippon Zeon Co., Ltd., "Quintac" is a registered trademark), TPE-SB series (manufactured by Sumitomo Chemical Co., Ltd.), Lavaron (manufactured by Mitsubishi Chemical Corporation, "Lavaron" is a registered trademark), Septon, Hybrar (all manufactured by Kuraray Co., Ltd., "Septon" and "Hybrar" are registered trademarks), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Leostomer, Actimer (all manufactured by Riken Technos Corporation, "Leostomer" and "Actimer" are registered trademarks), and the like.

[0073] (Olefin-based elastomer) The olefin-based elastomer is, for example, a polymer or copolymer of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-pentene, etc. Note that the olefin-based elastomer may have a hydroxyl group at the molecular terminal, and it is preferably one having a hydroxyl group at the molecular terminal. The olefin-based elastomer may be used alone or in combination of two or more. Examples of the olefin-based elastomer preferably include polyethylene, polybutadiene, hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisopropylene, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), etc. Further, copolymers of the α-olefins having 2 to 20 carbon atoms and non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, isoprene, etc. are also included. Furthermore, carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer is also included. As the olefin-based elastomer, those having a number average molecular weight of 1,000 to 5,000 are preferred, and those having a number average molecular weight of 1,500 to 3,500 are more preferred.

[0074] Commercially available products may be used as the olefin-based elastomer. Examples of commercially available products include Milastomer (trade name, manufactured by Mitsui Chemicals, Inc.), EXACT (trade name, manufactured by ExxonMobil), ENGAGE (trade name, manufactured by The Dow Chemical Company), Poly ip, Poly bd (trade name, manufactured by Idemitsu Kosan Co., Ltd.), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (trade name, manufactured by JSR Corporation), butadiene-acrylonitrile copolymer “NBR series” (trade name, manufactured by JSR Corporation), “XER series” of carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name, manufactured by JSR Corporation), BF-1000 of epoxidized polybutadiene obtained by partially epoxidizing polybutadiene (trade name, manufactured by Nippon Soda Co., Ltd.), PB-4700, PB-3600 (trade name, manufactured by Daicel Corporation), and the like.

[0075] (Polyester-based elastomer) Examples of the polyester-based elastomer include those obtained by polycondensing a dicarboxylic acid or its derivative and a diol compound or its derivative. The polyester-based elastomer may be used alone or in combination of two or more. 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 of the aromatic ring of the aromatic dicarboxylic acid are substituted with a methyl group, an ethyl group, a phenyl group, etc.; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, and dodecanedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; and the like. From the viewpoint of adhesion to the base material, it is also preferable to use dimer acid derived from natural products as the dicarboxylic acid. The dicarboxylic acid may be used alone or in combination of two or more. Examples of the derivative of the dicarboxylic acid include anhydrides of the dicarboxylic acid.

[0076] Examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol; aromatic diols represented by the following general formula (D-1), etc. The diol compound may be used alone or in combination of two or more.

[0077] [Chemical formula] (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-, -SO2-. R D1 and R D2 each independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms. p and q are each independently an integer of 0 to 4, and r is 0 or 1.)

[0078] In general formula (D-1), examples of the alkylene group having 1 to 10 carbon atoms represented by X D1 include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group, etc. From the viewpoints of via resolution, adhesion strength to plated copper, and electrical insulation reliability, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable. X D1 Examples of the alkylidene group having 2 to 10 carbon atoms represented by include an ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, etc. From the viewpoints of via resolution, adhesion strength to plated copper, and electrical insulation reliability, an isopropylidene group is preferable. X D1 Examples of the cycloalkylene group having 4 to 8 carbon atoms represented by include a cyclopentylene group, cyclohexylene group, cyclooctylene group, etc. X D1 Among these, as [X], an alkylene group having 1 to 10 carbon atoms or an alkylidene group having 2 to 10 carbon atoms is preferable, and a methylene group or an isopropylidene group is more preferable.

[0079] In the general formula (D-1), R D1 and R D2 Examples of the halogen atom represented by [R and R] include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. R D1 and R D2 Examples of the alkyl group having 1 to 12 carbon atoms represented by [R and R] 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, and the like. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. p and q are each independently an integer of 0 to 4, and each being 0 or 1 is preferable. r is 0 or 1, and either is acceptable. However, when r is 0, the structure is represented by the following general formula (D-1’).

Chemical formula

[0080] 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, resorcin, and the like.

[0081] Furthermore, as the polyester-based elastomer, a multi-block copolymer in which an aromatic polyester (for example, polybutylene terephthalate) part is used as a hard segment component and an aliphatic polyester (for example, polytetramethylene glycol) part is used as a soft segment component can also be used, and it is preferable to use such a multi-block copolymer. As such multi-block copolymers, there are various grades of commercially available products depending on the types, ratios, and molecular weights of the hard segments and soft segments. Specifically, "Hytrel (registered trademark)" (manufactured by Toray DuPont Co., Ltd.), "Pelprene (registered trademark)" (manufactured by Toyobo Co., Ltd.), "Esper (registered trademark)" (manufactured by Hitachi Chemical Co., Ltd.), etc. can be mentioned.

[0082] As the polyester-based elastomer, those having a number average molecular weight of 900 to 30,000 are preferable, those having a number average molecular weight of 1,000 to 25,000 are more preferable, and those having a number average molecular weight of 5,000 to 20,000 are even more preferable.

[0083] Commercially available products of polyester-based elastomers may be used. As commercially available products other than those mentioned above, for example, Teslac 2505-63 (manufactured by Hitachi Chemical Co., Ltd., "Teslac" is a registered trademark) etc. are commercially available.

[0084] (Urethane-based elastomer) As the urethane-based elastomer, for example, those containing a hard segment composed of a short-chain diol and a diisocyanate and a soft segment composed of a high molecular weight (long-chain) diol and a diisocyanate are preferably mentioned. The urethane-based elastomer may be used alone or in combination of two or more. Examples of the high molecular weight (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 high molecular weight (long-chain) diol is preferably 500 to 10,000. Examples of the short-chain diol include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, etc. The number-average molecular weight of the short-chain diol is preferably 48 to 500. As the urethane-based elastomer, those having a number-average molecular weight of 1,000 to 25,000 are preferred, those having a number-average molecular weight of 1,500 to 20,000 are more preferred, and those having a number-average molecular weight of 2,000 to 15,000 are even more preferred.

[0085] Commercially available products may be used as the urethane-based elastomer. Examples of the commercially available products include Nipolan 3116 (manufactured by Tosoh Corporation, "Nipolan" is a registered trademark), Pandex T-2185, T-2983N (manufactured by DIC Corporation), Miractran series (manufactured by Nippon Miractran Co., Ltd., "Miractran" is a registered trademark), Hitroid series (manufactured by Hitachi Chemical Co., Ltd., "Hitroid" is a registered trademark), etc.

[0086] (Polyamide-based elastomer) The polyamide-based elastomer is roughly classified into two types: a polyether block amide type using polyamide for the hard segment and polyether for the soft segment; and a polyether ester block amide type using polyamide for the hard segment and polyester for the soft segment. Specific examples of the polyamide-based elastomer include, for example, block copolymers using polyamide as the 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. as the soft segment component. The polyamide-based elastomer may be used alone or in combination of two or more. As the polyamide-based elastomer, those having a number-average molecular weight of 1,000 to 50,000 are preferred, and those having a number-average molecular weight of 2,000 to 30,000 are more preferred.

[0087] Polyamide-based elastomers may use commercially available products. Examples of commercially available products include UBE polyamide elastomers (manufactured by Ube Industries, Ltd.), Diamide (manufactured by Daicel-Evonik Co., Ltd., "Diamide" is a registered trademark), PEBAX (manufactured by Toray Industries, Inc.), Grilon ELY (manufactured by EMS Chemie Japan Co., Ltd., "Grilon" is a registered trademark), Novamid (manufactured by Mitsubishi Chemical Corporation), Glirast (manufactured by Toyobo Co., Ltd., "Glirast" is a registered trademark), and the like.

[0088] (Acrylic elastomer) Examples of the acrylic elastomer include polymers of raw material monomers mainly composed of acrylic esters. Preferred examples of the acrylic ester include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like. Further, as the crosslinking point monomer, those copolymerized with glycidyl methacrylate, allyl glycidyl ether, etc. may be used, and those copolymerized with acrylonitrile, ethylene, etc. may also be used. Specifically, acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like can be mentioned. The acrylic elastomer may be used alone or in combination of two or more. The acrylic elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000.

[0089] (Silicone elastomer) The silicone elastomer is an elastomer mainly composed of organopolysiloxane, and is classified into, for example, polydimethylsiloxane-based elastomer, polymethylphenylsiloxane-based elastomer, polydiphenylsiloxane-based elastomer, and the like. The silicone elastomer may be used alone or in combination of two or more. As the silicone-based elastomer, those having a number average molecular weight of 1,000 to 50,000 are preferred, and those having a number average molecular weight of 2,000 to 30,000 are more preferred.

[0090] Commercially available products may be used as the silicone-based elastomer. Examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (all of the above are manufactured by Toray Dow Corning Co., Ltd.).

[0091] (Other elastomers) Further, as the component (D), it may be an embodiment containing 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, polyetheretherketone resin, tetrafluoroethylene resin, polyacrylonitrile resin, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile.

[0092] (Content of component (D)) When the photosensitive resin composition of the present embodiment contains the component (D), its content is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, still more preferably 1 to 15% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 6% by mass based on the total solid content of the photosensitive resin composition. When the content of the component (D) is 0.5% by mass or more, the effect of improving the adhesion strength to electroless copper becomes sufficient, and the electrical insulation reliability tends to be further excellent. When the content of the component (D) is 20% by mass or less, the resolution of vias, the adhesion strength to electroless copper, and the electrical insulation reliability tend to be sufficient together.

[0093] <(E) Thermal polymerization initiator> The photosensitive resin composition of the present embodiment may contain a thermal polymerization initiator as the component (E). The thermal polymerization initiator is not particularly limited. For example, hydroperoxides such as diisopropylbenzene hydroperoxide "Perkyl P" (trade name, manufactured by NOF Corporation (the same applies hereinafter)), cumene hydroperoxide "Perkyl H", t-butyl hydroperoxide "Perbutyl H"; dialkyl peroxides such as α,α-bis(t-butylperoxy-m-isopropyl)benzene "Perbutyl P", dicumyl peroxide "Perkyl D", 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane "Perhex 25B", t-butylcumyl peroxide "Perbutyl C", di-t-butyl peroxide "Perbutyl D", 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 "Perhexyne 25B", t-butylperoxy-2-ethylhexanoate "Perbutyl O"; ketone peroxides; peroxyketals such as n-butyl 4,4-di-(t-butylperoxy)valerate "Perhex V"; diacyl peroxides; peroxydicarbonates; organic peroxides such as peroxy esters; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2,4-dimethylvaleronitrile); and the like. Among these, from the viewpoint of not inhibiting the photopolymerizability and having a great effect of improving the physical properties and characteristics of the photosensitive resin composition, dialkyl peroxides are preferred, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3 is more preferred. The thermal polymerization initiator may be used alone or in combination of two or more.

[0094] (Content of component (E)) When the photosensitive resin composition of this embodiment contains component (E), its content is not particularly limited, but based on the total amount of the resin components of the photosensitive resin composition, it is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.03 to 2% by mass. If it is 0.01% by mass or more, sufficient thermal curing tends to be achieved, and if it is 5% by mass or less, the photosensitive characteristics and heat resistance tend to be good.

[0095] <(F) Inorganic filler> The photosensitive resin composition of this embodiment may contain an inorganic filler as the (F) component, and preferably contains an inorganic filler. By containing the inorganic filler, the thermal expansion can be reduced, and the possibility of warpage is decreased. In the thermosetting resin composition that has been conventionally used as the interlayer insulating layer of a multilayer printed wiring board, the thermal expansion has been reduced by containing an inorganic filler. However, when an inorganic filler is contained in the photosensitive resin composition, it is difficult to reduce the thermal expansion by containing a large amount because the inorganic filler causes light scattering and becomes an obstacle to development. Thus, there are new problems unique to the photosensitive resin composition with respect to containing an inorganic filler. However, the photosensitive resin composition of this embodiment tends to have high resolution of vias even when a large amount of inorganic filler is contained. Therefore, with the photosensitive resin composition of this embodiment, it is possible to achieve both low thermal expansion and high resolution of vias.

[0096] (F) components include, for example, 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·Al2O3), 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. The (F) component may be used alone or in combination of two or more kinds.

[0097] (F) component's average particle diameter is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, still more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm from the viewpoint of via resolution. Here, the average particle diameter of the (F) component is the volume average particle diameter of the inorganic filler in the state of being dispersed in the photosensitive resin composition, and is taken as the value obtained by measuring as follows. First, after diluting (or dissolving) the photosensitive resin composition 1,000 times with methyl ethyl ketone, using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5), in accordance with the international standard ISO13321, with a refractive index of 1.38, the particles dispersed in the solvent are measured, and the particle diameter at the integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle diameter (volume average particle diameter). Also, for the (F) component contained in the photosensitive resin film provided on the carrier film and the interlayer insulating layer, after diluting (or dissolving) 1,000 times (volume ratio) with a solvent as described above, it can be measured by using the above submicron particle analyzer.

[0098] As the (F) component, from the viewpoints of heat resistance and low thermal expansion, it preferably contains silica, and more preferably is silica. Also, from the viewpoint of improving the dispersibility of the inorganic filler in the photosensitive resin composition by the anti-aggregation effect, those surface-treated with alumina or an organic silane-based compound may be used.

[0099] ((Content of the (F) component)) When the photosensitive resin composition of this embodiment contains the (F) component, its content is not particularly limited, but based on the total solid content of the photosensitive resin composition, it is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, still more preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass. If the content of the (F) component is within the above range, mechanical strength, heat resistance, via resolution, etc. can be improved.

[0100] <(G) pigment> The photosensitive resin composition of this embodiment may contain a pigment as the (G) component according to the desired color for adjusting photosensitivity and the like. As the (G) component, a colorant that develops a desired color may be appropriately selected and used. For example, known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black are preferably mentioned.

[0101] (Content of (G) component) When the photosensitive resin composition of this embodiment contains the (G) component, its content is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and still more preferably 0.05 to 2% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of adjusting photosensitivity and the like.

[0102] <(H) curing agent> The photosensitive resin composition of this embodiment may contain a curing agent from the viewpoint of further improving various properties such as heat resistance, adhesion strength to electroless copper, and chemical resistance. In particular, when the (C) thermosetting resin contains an epoxy resin, it is preferable to contain an epoxy resin curing agent as the 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-xylenediamine, 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; tertiary amines such as trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyphenols such as polyvinylphenol, brominated polyvinylphenol, phenol novolak, and alkylphenol novolak; 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 aforementioned polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and the like. Among these, polyamines are preferred, and melamine is more preferred, from the viewpoint of further improving various properties such as heat resistance, adhesion strength to electrodeposited copper, and chemical resistance. When the photosensitive resin composition of the present embodiment contains the component (H), its content is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, still more preferably 0.03 to 3% by mass, based on the total amount of the resin components of the photosensitive resin composition.

[0103] <Diluent> A diluent can be used in the photosensitive resin composition of the present embodiment as needed. As the diluent, for example, organic solvents and the like can be used. As the organic solvent, for example, 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; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. The diluent may be used alone or in combination of two or more.

[0104] (Content of diluent) 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% by mass, more preferably 50 to 80% by mass, still more preferably 55 to 65% by mass. By adjusting the amount of the diluent used in this way, the coatability of the photosensitive resin composition is improved, and the formation of a finer pattern becomes possible.

[0105] <Other additives> The photosensitive resin composition of this embodiment may contain, as necessary, polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, etc.; thickeners such as benton, montmorillonite, etc.; defoamers such as silicone-based defoamers, fluorine-based defoamers, vinyl resin-based defoamers, etc.; silane coupling agents; and various other known and commonly used additives. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, and phosphate compounds of phosphorus-based compounds, aromatic condensed phosphoric acid esters, halogen-containing condensed phosphoric acid esters, etc. can be contained.

[0106] The photosensitive resin composition of this embodiment can be obtained by kneading and mixing each component with a roll mill, bead mill, etc. Here, the photosensitive resin composition of this embodiment may be used in a liquid state or in a film state. When used in a liquid state, the coating method of the photosensitive resin composition of this embodiment is not particularly limited, and examples include various coating methods such as printing methods, spin coating methods, spray coating methods, jet dispensing methods, inkjet methods, dipping coating methods, etc. Among these, from the perspective of more easily forming the photosensitive layer, it can be appropriately selected from printing methods and spin coating methods. Also, when used in a film state, for example, it can be used in the form of a photosensitive resin film described later. In this case, a photosensitive layer with a desired thickness can be formed by laminating it on a carrier film using a laminator or the like. Note that using it in a film state is preferable because the manufacturing efficiency of a multilayer printed wiring board is higher.

[0107] [Photosensitive Resin Film, Photosensitive Resin Film for Interlayer Insulation Layer] The photosensitive resin film of this embodiment is a photosensitive layer that will later become an interlayer insulation layer and is composed of the photosensitive resin composition of this embodiment. The photosensitive resin film of this embodiment may be in a mode where the photosensitive resin film is provided on a carrier film. The thickness (thickness after drying) of the photosensitive resin film (photosensitive layer) is not particularly limited, but from the viewpoint of thinning of the multilayer printed wiring board, it is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 5 to 40 μm.

[0108] The photosensitive resin film of the present embodiment can be obtained, for example, by applying and drying the photosensitive resin composition of the present embodiment on a carrier film with 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, thereby forming a photosensitive layer that will later become an interlayer insulating layer. Examples of the carrier film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; and polyolefin films such as polypropylene film and polyethylene film. The thickness of the carrier film may be appropriately selected from the range of 5 to 100 μm, preferably 5 to 60 μm, and more preferably 15 to 45 μm.

[0109] In addition, a protective film can be provided on the surface of the photosensitive layer of the photosensitive resin film of the present embodiment on the side opposite to the surface in contact with the carrier film. As the protective film, for example, polymer films such as polyethylene and polypropylene can be used. Also, a polymer film similar to the above-described carrier film may be used, or a different polymer film may be used.

[0110] For drying the coating film formed by applying the photosensitive resin composition, a hot air dryer, a far-infrared dryer, or a dryer using near-infrared rays can be used. The drying temperature is preferably 60 to 150 °C, more preferably 70 to 120 °C, and still more preferably 80 to 100 °C. The drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and still more preferably 5 to 20 minutes. From the viewpoint of avoiding diffusion of the diluent in the manufacturing process of the multilayer printed wiring board, the content of the residual diluent in the photosensitive resin film after drying is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less.

[0111] The photosensitive resin film of this embodiment is excellent in via resolution, adhesion strength to electroless copper, crack resistance, and electrical insulation reliability, and thus is suitable as an interlayer insulating layer of a multilayer printed wiring board. That is, the present invention also provides a photosensitive resin film for an interlayer insulating layer. Note that the photosensitive resin film for an interlayer insulating layer can also be referred to as an interlayer insulating photosensitive film.

[0112] [Multilayer Printed Wiring Board and Method for Manufacturing the Same] 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 this embodiment. There is no particular limitation on the manufacturing method of the multilayer printed wiring board of this embodiment as long as it has a step of forming an interlayer insulating layer using the photosensitive resin composition of this embodiment. For example, it can be easily manufactured by the following method for manufacturing a multilayer printed wiring board of this embodiment.

[0113] 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 (photosensitive resin film for an interlayer insulating layer) of this embodiment will be described with appropriate reference to FIG. 1. The 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 this embodiment on 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 "photo via forming step (2)"). Step (3): A step of roughening the vias and the interlayer insulating layer (hereinafter referred to as "roughening treatment 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)").

[0114] (Lamination process (1)) The lamination process (1) is a process of laminating the photosensitive resin film (photosensitive resin film for interlayer insulation layer) of the present embodiment on one or both sides of a circuit board (substrate 101 having a circuit pattern 102) using a vacuum laminator. Examples of the vacuum laminator include a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressure type 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.

[0115] When a protective film is provided on the photosensitive resin film, after peeling or removing the protective film, it can be laminated by pressure-bonding to the circuit board while applying pressure and heat so that the photosensitive resin film is in contact with the circuit board. This lamination can be carried out, for example, after preheating the photosensitive resin film and the circuit board as required, under reduced pressure with a pressure-bonding temperature of 70 to 130°C, a pressure-bonding pressure of 0.1 to 1.0 MPa, and an air pressure of 20 mmHg (26.7 hPa) or less, but it is not particularly limited to these conditions. Also, the lamination method may be a batch type or a continuous type using a roll. Finally, the photosensitive resin film laminated on the circuit board (hereinafter sometimes referred to as a photosensitive layer) is cooled to near room temperature to form an interlayer insulation layer 103. The carrier film may be peeled off here, or may be peeled off after exposure as described later.

[0116] (Photo via formation process (2)) In the photo via formation step (2), at least a part of the photosensitive resin film laminated on the circuit board is exposed and then developed. By the exposure, the portion irradiated with the actinic ray is photocured to form a pattern. There is no particular limitation on the exposure method. For example, a method of irradiating the actinic ray in an image shape through a negative or positive mask pattern called an artwork (mask exposure method) may be adopted, or a method of irradiating the actinic ray in an image shape by a direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be adopted. As the light source of the actinic ray, a known light source can be used. Specifically, as the light source, gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and argon lasers; solid lasers such as YAG lasers; those that effectively emit ultraviolet rays or visible light such as semiconductor lasers; and the like can be mentioned. The exposure amount is appropriately selected according to the light source used, the thickness of the photosensitive layer, etc. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, when the thickness of the photosensitive layer is 1 to 100 μm, usually, 10 to 1,000 mJ / cm 2 is preferable, and 15 to 500 mJ / cm 2 is more preferable.

[0117] In development, the uncured portion of the photosensitive layer is removed from the substrate, whereby an interlayer insulating layer made of a photocured cured product is formed on the substrate. When a carrier film exists on the photosensitive layer, the carrier film is removed and then the unexposed portion is removed (developed). As the development method, there are wet development and dry development, and either can be adopted, but wet development is widely used, and wet development can also be adopted in this embodiment. In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the development method include methods using a dip method, a paddle method, a spray method, brushing, slapping, scraping, oscillating immersion, etc. Among these, from the viewpoint of improving resolution, the spray method is preferable, and among the spray methods, the high-pressure spray method is more preferable. Development may be carried out by one method, or may be carried out in combination of two or more methods. The composition of the developer is appropriately selected according to the composition of the photosensitive resin composition. For example, an alkaline aqueous solution, an aqueous developer, and an organic solvent-based developer can be mentioned, and among these, an alkaline aqueous solution is preferable.

[0118] In the photovia formation step (2), after exposure and development, post-UV curing with an exposure amount of about 200 to 10,000 mJ / cm 2 (preferably 500 to 5,000 mJ / cm 2 ) and post-thermal curing at a temperature of about 60 to 250°C (preferably 120 to 200°C) may be carried out as necessary to further cure the interlayer insulating layer, and it is preferably done so. As described above, an interlayer insulating layer having vias 104 is formed. There is no particular limitation on the shape of the vias. When described in terms of the cross-sectional shape, for example, a square, an inverted trapezoid (the upper side is longer than the lower side), etc. can be mentioned. When described in terms of the shape seen from the front (the direction in which the via bottom can be seen), a circle, a square, etc. can be mentioned. In the formation of vias by the photolithography method in this embodiment, vias having a cross-sectional shape of an inverted trapezoid (the upper side is longer than the lower side) can be formed. In this case, it is preferable because the adhesion property to the via wall surface of the plated copper is improved.

[0119] The size (diameter) of the vias formed by this step can be 60 μm or less, and further, it can be less than 40 μm or 30 μm or less, and can be made smaller than the size of vias produced by laser processing. There is no particular limitation on the lower limit value of the size (diameter) of the vias formed by this step, but it may be 15 μm or more, or may be 20 μm or more. However, the size (diameter) of the vias formed by this process is not necessarily limited to 60 μm or less. For example, it may be about 200 μm or less, and can be arbitrarily selected within the range of, for example, 15 to 300 μm.

[0120] (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 solution. When smearing occurs in the photo via formation step (2), the smear may be removed with the roughening solution. The roughening treatment and the removal of the smear can be performed simultaneously. Examples of the roughening solution include a chromium / sulfuric acid roughening solution, an alkaline permanganic acid roughening solution (e.g., a sodium permanganate roughening solution, etc.), and a sodium fluoride / chromium / sulfuric acid roughening solution. By the roughening treatment, an anchor of unevenness is formed on the surfaces of the vias and the interlayer insulating layer.

[0121] (Circuit pattern formation step (4)) The circuit pattern formation 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 formation of the circuit pattern is preferably carried out by a semi-additive process. Conductivity of the vias is achieved together with the formation of the circuit pattern by the semi-additive process. In the semi-additive process, first, electroless copper plating treatment is performed using a palladium catalyst or the like on the entire surface of the via bottom, the via wall surface, and the interlayer insulating layer after the roughening treatment step (3) to form a seed layer 105. The seed layer is for forming a power supply layer for performing electrolytic copper plating, and is preferably formed with a thickness of about 0.1 to 2.0 μm. If the thickness of the seed layer is 0.1 μm or more, the connection reliability during electrolytic copper plating can be suppressed from decreasing. If it is 2.0 μm or less, it is not necessary to increase the etching amount when flash etching the seed layer between the wirings, and the damage to the wirings during etching can be suppressed.

[0122] The electroless copper plating treatment is performed by depositing metallic copper on the surfaces of vias and the interlayer insulating layer through the reaction between copper ions and a reducing agent. The electroless plating treatment method and the electrolytic plating treatment method may be well-known methods and are not particularly limited. However, the catalyst for the electroless plating treatment step is preferably a palladium-tin mixed catalyst, and the primary particle size of the catalyst is preferably 10 nm or less. Also, as the plating composition for the electroless plating treatment step, it is preferable to contain hypophosphorous acid as a reducing agent. Commercially available products can be used as the electroless copper plating solution. Examples of commercially available products include "MSK-DK" manufactured by Atotech Japan Co., Ltd., "Surcup (registered trademark) PEA ver.4" series manufactured by Uemura Kogyo Co., Ltd., and the like.

[0123] After the electroless copper plating treatment, a dry film resist is thermocompression-bonded onto the electroless copper plating using a roll laminator. The thickness of the dry film resist must be higher than the wiring height after electroplating copper. From this perspective, a dry film resist with a thickness of 5 to 30 μm is preferable. As the dry film resist, the "Fotec" series manufactured by Hitachi Chemical Co., Ltd. and the like are used. After the thermocompression-bonding of the dry film resist, for example, the dry film resist is exposed through a mask on which a desired wiring pattern is drawn. The exposure can be performed using the same apparatus and light source as those that can be used when forming vias in the photosensitive resin film. After exposure, the carrier film on the dry film resist is peeled off, and development is performed using an alkaline aqueous solution to remove the unexposed portions and form a resist pattern 106. Thereafter, an operation of removing the development residue of the dry film resist using plasma or the like may be performed as necessary. After development, electroplating copper is performed to form a copper circuit layer 107 and perform via filling.

[0124] After electroplating with copper, the dry film resist is removed using an alkaline aqueous solution or an amine-based stripper. After removing the dry film resist, the seed layer between the wirings is removed (flash etching). The flash etching is performed using an acidic solution such as sulfuric acid and hydrogen peroxide and an oxidizing solution. Specifically, "SAC" manufactured by JCU Corporation, "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc., etc. are mentioned. After flash etching, if necessary, the removal of palladium or the like adhering to the portion between the wirings is performed. The removal of palladium can preferably be performed using an acidic solution such as nitric acid and hydrochloric acid.

[0125] After removing the dry film resist or after the flash etching process, preferably a post-bake treatment is performed. The post-bake treatment sufficiently thermosets the unreacted thermosetting components, and thereby further improves the electrical insulation reliability, curing characteristics, and adhesion strength to the plated copper. The thermosetting conditions vary depending on the type of the resin composition and the like, but it is preferable that the curing temperature is 150 to 240°C and the curing time is 15 to 100 minutes. By the post-bake treatment, one set of the manufacturing process of the printed wiring board by the photo via method is completed, but the substrate is manufactured by repeating this process according to the required number of the interlayer insulation layers. And preferably, a solder resist layer 108 is formed on the outermost layer.

[0126] As described above, the method for manufacturing a multilayer printed wiring board for forming vias using the photosensitive resin composition of the present embodiment has been described. Since the photosensitive resin composition of the present embodiment is excellent in pattern resolution, for example, it is also suitable for forming a cavity for incorporating a chip or a passive element or the like. The cavity can be suitably formed, for example, in the description of the multilayer printed wiring board described above, by setting the drawing pattern when exposing the photosensitive resin film to form a pattern to be able to form a desired cavity. Furthermore, the photosensitive resin composition of the present embodiment is also useful as a surface protective film such as a solder resist.

[0127] [Semiconductor Package] The present invention also provides a semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board of the present embodiment. The semiconductor package of the present embodiment can be manufactured by mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on the multilayer printed wiring board of the present invention and sealing the semiconductor elements with a sealing resin or the like.

Examples

[0128] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The photosensitive resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were evaluated for their properties by the methods shown below.

[0129] [1. Evaluation of via resolution] (1-1) Preparation of evaluation laminate The copper foil surface of a printed wiring board substrate (manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-679") obtained by laminating a 12-μm-thick copper foil on a glass epoxy substrate was treated with a roughening pretreatment solution (manufactured by Meck Co., Ltd., product name "CZ-8100"), followed by washing with water and drying to obtain a roughening-pretreated printed wiring board substrate. Next, the protective film was peeled off from the carrier film and the photosensitive resin film with a protective film manufactured in each example and comparative example, and the exposed photosensitive resin film was placed in contact with the copper foil of the roughening-pretreated printed wiring board substrate. Then, a laminating process was performed using a press-type vacuum laminator (manufactured by Namek Co., Ltd., product name "MVLP-500"). The laminating conditions were a press hot plate temperature of 70°C, a vacuum drawing time of 20 seconds, a laminating press time of 30 seconds, an air pressure of 4 kPa or less, and a crimping pressure of 0.4 MPa. After the laminating process, it was left at room temperature for 1 hour or more to obtain an evaluation laminate in which the photosensitive resin film and the carrier film were laminated in this order on the copper foil surface of the printed wiring board substrate. (1-2) Measurement of sensitivity of photosensitive resin film After peeling and removing the carrier film of the laminated body for evaluation obtained above, a 41-step tablet was placed, and exposure was performed using a direct imaging exposure apparatus "DXP-3512" (manufactured by Okou Seisakusho Co., Ltd.) with an ultra-high pressure mercury lamp as the light source. The exposure pattern used was a pattern in which dots were arranged in a grid (dot diameter: distance between dot centers = 1:2). The diameter of the dots was changed in 5-μm increments in the range of φ30 to 100 μm. After exposure, the sample was left at room temperature for 30 minutes, and then the photosensitive resin composition in the unexposed area was spray-developed for 60 seconds using a 1 mass% aqueous sodium carbonate solution at 30°C. After development, the exposure energy amount at which the number of remaining gloss steps of the 41-step tablet was 8.0 was defined as the sensitivity of the photosensitive resin film (unit: mJ / cm 2 ). Using the pattern exposed at this sensitivity, the resolution of the vias provided in the photosensitive resin film was evaluated according to the following evaluation criteria. (1-3) Evaluation of resolution For the evaluation of resolution, the photosensitive resin film was exposed at the sensitivity measured in (1-2) above, that is, the exposure energy amount at which the number of steps was 8.0, and then spray-developed. After that, the via pattern was observed using an optical microscope and evaluated according to the following criteria. The above state of "open" refers to a state in which the copper foil of the base material for printed wiring boards can be confirmed when observing the via portion of the dot pattern using an optical microscope. A judgment of "A" indicates good characteristics. A: The φ60-μm via portion of the dot pattern is open. B: The φ60-μm via portion of the dot pattern is not open. C: It did not cure by light.

[0130] [2. Evaluation of adhesive strength (peel strength) with copper plating] While peeling the protective layer of the above photosensitive film, a press-type vacuum laminator (manufactured by Naiki Seisakusho Co., Ltd., product name "MVLP-500") was used on a copper-clad laminate substrate with a thickness of 1.0 mm. Lamination was performed at a pressure of 0.4 MPa, a press hot plate temperature of 80°C, a vacuum drawing time of 25 seconds, a laminate press time of 25 seconds, and an air pressure of 4 kPa or less to obtain a laminate. Regarding the obtained laminate, using a parallel light exposure machine (manufactured by Okou Seisakusho Co., Ltd., trade name "EXM-1201") with an ultra-high pressure mercury lamp as the light source, full-surface exposure was performed at 500 mJ / cm 2 Then, using an ultraviolet exposure device, exposure was performed at an exposure dose of 2,000 mJ / cm 2 and heated at 170 °C for 1 hour to obtain a cured film on the copper-clad laminate substrate.

[0131] Next, in order to chemically roughen the surface of the cured product, an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L and sodium hydroxide: 5 g / L was prepared as a swelling solution, heated to 70 °C, and immersed for 10 minutes. Next, as a roughening solution, an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L was prepared, heated to 70 °C, and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (tin chloride (SnCl2): 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 °C, and immersed for 5 minutes to reduce potassium permanganate. Next, the surface of the desmian-treated cured product was treated with an alkaline cleaner (Cleaner Securigrant 902) at 60 °C for 5 minutes for degreasing and cleaning. After cleaning, the desmian-treated cured product was treated with a pre-dip solution (Pre-dip Neogant B) at 23 °C for 1 minute. Then, the cured product was treated with an activator solution (Activator Neogant 834) at 35 °C for 5 minutes, and then the cured product was treated with a reducing solution (Reducer Neogant WA) at 30 °C for 5 minutes. The laminate thus obtained was placed in a chemical copper solution (Basic Print Gant MSK-DK, Copper Print Gant MSK, Stabilizer Print Gant MSK), and electroless plating was performed until the plating thickness reached about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 °C for 30 minutes to remove the remaining hydrogen gas. Then, copper sulfate electrolytic plating was performed, and annealing treatment was performed at 180 °C for 60 minutes to form a conductor layer with a thickness of 25 μm.

[0132] Regarding the laminate on which the conductor layer was formed as described above, in accordance with JIS C6481 (1996), the vertical peel strength was measured at 23 °C and evaluated according to the following evaluation criteria. A: The adhesive strength with the plated copper was 0.40 kN / m or more. B: The adhesive strength with the plated copper was less than 0.40 kN / m and 0.30 kN / m or more. C: The adhesive strength with the plated copper was less than 0.30 kN / m.

[0133] [3. Evaluation of Electrical Insulation Reliability (HAST Resistance)] In the above [2. Evaluation of Adhesive Strength (Peel Strength) with Plated Copper], the same operations were performed except that a conductor layer with a thickness of 35 μm was formed instead of a conductor layer with a thickness of 25 μm, and a laminate with a formed conductor layer was obtained. The formed conductor layer was etched to form a circular electrode with a diameter of φ6 mm. Subsequently, a photosensitive solder resist film "FZ-2700GA" (manufactured by Hitachi Chemical Co., Ltd., trade name) with a layer thickness of 25 μm was formed on the electrode and the cured film using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., trade name "MVLP-500") at a pressure bonding pressure of 0.4 MPa, a press hot plate temperature of 80 °C, a vacuum evacuation time of 25 seconds, a laminate press time of 40 seconds, and an air pressure of 4 kPa or less to obtain a laminate for evaluation.

[0134] Regarding the laminate for evaluation obtained as described above, using a parallel light exposure machine (manufactured by OAK Corporation, trade name "EXM-1201") with an ultra-high pressure mercury lamp as the light source, it was exposed over the entire surface at 500 mJ / cm 2 . Next, it was exposed using an ultraviolet exposure device at an exposure dose of 2,000 mJ / cm 2 and heated at 160 °C for 1 hour to obtain a cured film. Subsequently, wiring was performed so that the circular electrode was the + electrode and the copper foil on the side where the circular electrode of the copper-clad laminate substrate was formed was the - electrode, and it was exposed to 135 °C, 85%, 5.5 V conditions for 200 hours using a pressure cooker (model name "Unsaturated Super Accelerated Life Test Device PC-422RP", manufactured by Hirayama Seisakusho Co., Ltd.). The resistance value between the electrodes was measured and evaluated according to the following evaluation criteria. A: The resistance value after 200 hours was 10×10 7 Ω or more. B: The resistance value after 200 hours was 10×107 less than Ω and 10×10 6 and more than 10 Ω. C: The resistance value after 200 hours was less than 10×10 6 Ω.

[0135] <Synthesis Example 1> Synthesis of an acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 1 [(A1-1) component] 350 parts by mass of a dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "XD-1000", epoxy equivalent 252 g / eq, softening point 74.2 °C, corresponding to the (a1) component, represented by the general formula (a1-1). The number of ring-forming carbon atoms of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to the (a2) component), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90 °C, and reacted by stirring to dissolve the mixture. Next, the obtained solution was cooled to 60 °C, 2 parts by mass of triphenylphosphine was added, heated to 100 °C, and reacted until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a3) component) and 85 parts by mass of carbitol acetate were added, heated to 80 °C, and reacted for 6 hours. Thereafter, it was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate (corresponding to the (A1-1) component. Hereinafter, referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 1") having a solid content concentration of 73% by mass.

[0136] <Synthesis Example 2> Synthesis of an acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 2 [(A1-1) component] 350 parts by mass of a dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, "EPICLON (registered trademark) HP-7200", epoxy equivalent 254 - 264 g / eq, softening point 56 - 66 °C, corresponding to the (a1) component, represented by the general formula (a1-1). The number of ring-forming carbon atoms of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to the (a2) component), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90 °C, and reacted by stirring to dissolve the mixture. 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 solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a3) component) 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 having a solid content concentration of 74% by mass (corresponding to the (A1-1) component. Hereinafter, it is referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 2").

[0137] <Synthesis Example 3> Synthesis of Acid-Modified Ethylenically Unsaturated Group-Containing Epoxy Derivative Containing No Alicyclic Skeleton 350 parts by mass of bisphenol F novolak type epoxy resin (manufactured by DIC Corporation, "EXA-7376", corresponding to the (a21) component), 70 parts by mass of acrylic acid (corresponding to the (a22) component), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90°C, and reacted by stirring to dissolve the mixture. 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 solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a23) component) 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 bisphenol F type epoxy acrylate having a solid content concentration of 73% by mass (corresponding to the (A2-1) component. Hereinafter, it is referred to as "acid-modified ethylenically unsaturated group-containing epoxy derivative 3").

[0138] <Examples 1 to 3, Comparative Examples 1 to 2> (Preparation of Photosensitive Resin Composition) The composition was formulated according to the formulation composition and formulation amounts shown in Table 1 and kneaded with a three-roll mill to prepare a photosensitive resin composition. In each example, carbitol acetate was appropriately added to adjust the concentration, and a photosensitive resin composition having a solid content concentration of 60% by mass was obtained. (Preparation of Photosensitive Resin Film) A polyethylene terephthalate film with a thickness of 25 μm (G2-25, manufactured by Teijin Limited, trade name) was used as a carrier film. Onto this carrier film, the photosensitive resin composition prepared in each example was applied so that the film thickness after drying would be 25 μm, and it was dried at 100 °C for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a biaxially oriented polypropylene film (MA-411, manufactured by Oji F-Tex Corporation, trade name) was laminated as a protective film onto the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, and a photosensitive resin film with the carrier film and the protective film laminated was prepared. Using the prepared photosensitive resin film, each evaluation was carried out according to the above method. The results are shown in Table 1.

[0139]

Table 1

[0140] Each component used in each example is as follows. (Component (A); · Epoxy derivative 1 containing an acid-modified ethylenically unsaturated group and an alicyclic skeleton [(A1-1) component]: The one obtained in Synthesis Example 1 was used. · Epoxy derivative 2 containing an acid-modified ethylenically unsaturated group and an alicyclic skeleton [(A1-1) component]: The one obtained in Synthesis Example 2 was used. · Epoxy derivative 3 containing an acid-modified ethylenically unsaturated group [(A2-1) component]: The one obtained in Synthesis Example 3 was used. · Dipentaerythritol pentaacrylate [(Aiii) component] (Component (B); · Photoinitiator 1: 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, acetophenones · Photoinitiator 2: 2,4-Diethylthioxanthone, thioxanthones (Component (C); · Biphenyl-type epoxy resin: "YX-4000" (manufactured by Mitsubishi Chemical Corporation, trade name) · Epoxidized polybutadiene: "PB3600" (manufactured by Daicel Chemical Industries, Ltd., trade name) (D) component; · Polyester: "Esper (registered trademark) 1108" (manufactured by Hitachi Chemical Co., Ltd., trade name) (F) component; · Silica: "SFP-20M" (manufactured by Denka Co., Ltd., average particle size 0.3 μm, trade name)

[0141] From Table 1, it can be seen that in Examples 1 to 3, excellent results were obtained in terms of via resolution, adhesion strength to plated copper, and electrical insulation reliability. On the other hand, in Comparative Examples 1 and 2 where the (A1) component was not contained, the adhesion strength to plated copper and electrical insulation reliability were insufficient.

[0142] Separately, a photosensitive resin composition described later was prepared, and the resolution and crack resistance were evaluated according to the following method. [4. Evaluation of Via Resolution] (4-1) Preparation of Evaluation Laminate The copper foil surface of a printed wiring board substrate (manufactured by Hitachi Chemical Co., Ltd., trade name "MCL-E-679") obtained by laminating a 12-μm-thick copper foil on a glass epoxy substrate was polished with an abrasive brush, washed with water, dried, and a printed wiring board substrate subjected to roughening pretreatment was obtained. Next, the protective film was peeled off from the carrier film and the photosensitive resin film with a protective film manufactured in each Example and Comparative Example, and the exposed photosensitive resin film was placed in contact with the copper foil of the above-mentioned printed wiring board substrate subjected to roughening pretreatment. Then, a laminating treatment was performed using a press-type vacuum laminator (manufactured by Namiki Seisakusho Co., Ltd., trade name "MVLP-500"). The laminating conditions were a press hot plate temperature of 70 °C, a vacuum drawing time of 20 seconds, a laminating press time of 20 seconds, an air pressure of 4 kPa or less, and a crimping pressure of 0.4 MPa. After the laminating treatment, it was left at room temperature for 1 hour or more to obtain an evaluation laminate in which the photosensitive resin film and the carrier film were laminated in this order on the copper foil surface of the printed wiring board substrate. (4-2) Measurement of Sensitivity of Photosensitive Resin Film After peeling off and removing the carrier film of the laminate for evaluation obtained above, 41-step tablet was placed, and exposure was performed using a direct imaging exposure apparatus "DXP-3512" (manufactured by Okou Seisakusho Co., Ltd.) with an ultra-high pressure mercury lamp as a light source. The exposure pattern used was a pattern in which squares were arranged in a lattice (length of one side: distance between the centers of the squares = 1:2). After exposure, it was left at room temperature for 30 minutes, then the polyethylene terephthalate of the support was removed, and the photosensitive resin composition in the unexposed area was spray-developed for 60 seconds using a 1 mass% aqueous sodium carbonate solution at 30°C. After development, the exposure energy amount at which the number of remaining gloss steps of the 41-step tablet becomes 10.0 was defined as the sensitivity of the photosensitive resin film (unit: mJ / cm 2 )). Using the pattern exposed at this sensitivity, the resolution of the vias provided in the photosensitive resin film was evaluated according to the following evaluation criteria. (4-3) Evaluation of Resolution For the evaluation of resolution, the photosensitive resin film was exposed at the sensitivity of the photosensitive resin film measured in the above (4-2), that is, the exposure energy amount at which the number of steps becomes 10.0, and then after spray development, the via pattern was observed using an optical microscope and evaluated according to the following criteria. The above state of "open" refers to a state where the copper foil of the base material for printed wiring boards can be confirmed when observing the via portion of the dot pattern using an optical microscope. The determination of "A" indicates good characteristics. A: The dimension of the bottom of the via pattern with one side of 60 μm is 50 μm or more on one side. B: The dimension of the bottom of the via pattern with one side of 60 μm is 40 μm or more and less than 50 μm on one side. C: The dimension of the bottom of the via pattern with one side of 60 μm is 30 μm or more and less than 40 μm on one side.

[0143] [5. Evaluation of Crack Resistance] The laminate for evaluation prepared in the same manner as in the above (4-1) was exposed to the atmosphere at -65°C for 15 minutes, then heated at a heating rate of 180°C / min, and then exposed to the atmosphere at 150°C for 15 minutes, and then cooled at a cooling rate of 180°C / min. This thermal cycle was repeated 1,000 times. Subsequently, the laminated body for evaluation was observed at 100-fold magnification with a metal microscope at 10 arbitrary locations at the opening of a 2 mm square via, and the degree of cracking and delamination was evaluated according to the following evaluation criteria. A: No cracking or delamination was observed at all. B: Cracking and delamination were observed at 1 or 2 locations out of 10. C: Cracking and delamination were observed at 3 locations out of 10. D: Cracking and delamination were observed at 4 or more locations out of 10.

[0144] <Synthesis Examples 4 - 5> Synthesis of Acid-Modified Ethylenically Unsaturated Group and Alicyclic Skeleton-Containing Epoxy Derivatives 4 - 5 [(Component (A1-1))] 350 parts by mass of a dicyclopentadiene-type epoxy resin (manufactured by DIC Corporation, "EPICLON (registered trademark) HP-7200", epoxy equivalent 254 - 264 g / eq, softening point 56 - 66 °C, corresponding to component (a1) and represented by the general formula (a1-1); number of ring-forming carbon atoms of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to component (a2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90 °C, and reacted by stirring to dissolve the mixture. Next, the obtained solution was cooled to 60 °C, 2 parts by mass of triphenylphosphine was added, heated to 100 °C, and reacted until the acid value of the solution reached 1 mg KOH / g. To the solution after the reaction, tetrahydrophthalic anhydride (corresponding to component (a3)) and carbitol acetate were added, heated to 80 °C, and reacted for about 6 hours. The amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the resulting acid-modified dicyclopentadiene-type epoxy acrylate would be 60 mg KOH / g and 80 mg KOH / g. Thereafter, it was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having a solid acid value of 60 mgKOH / g (corresponding to the component (A1-1); hereinafter referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 4") and an acid-modified dicyclopentadiene type epoxy acrylate having a solid acid value of 80 mgKOH / g (corresponding to the component (A1-1); hereinafter referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 5").

[0145] <Synthesis Examples 6 to 8> Synthesis of Acid-Modified Ethylenically Unsaturated Group and Alicyclic Skeleton-Containing Epoxy Derivatives 6 to 8 [(A1-1) Component] 350 parts by mass of a dicyclopentadiene type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., "XD-1000", epoxy equivalent 252 g / eq, softening point 74.2 °C, corresponding to the component (a1) and represented by the general formula (a1-1); number of ring-forming carbon atoms of the alicyclic skeleton: 10), 70 parts by mass of acrylic acid (corresponding to the component (a2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90 °C and stirred to cause a reaction to dissolve the mixture. 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 solution after the reaction, tetrahydrophthalic anhydride (corresponding to the component (a3)) and carbitol acetate were added, and the mixture was heated to 80 °C and reacted for about 6 hours. The amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the obtained acid-modified dicyclopentadiene type epoxy acrylate would be 60 mgKOH / g, 80 mgKOH / g, or 100 mgKOH / g. Thereafter, it was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having an acid value of the solid content of 60 mgKOH / g (corresponding to the component (A1-1); hereinafter referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 6"), an acid-modified dicyclopentadiene type epoxy acrylate having an acid value of the solid content of 80 mgKOH / g (corresponding to the component (A1-1); hereinafter referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 7"), and an acid-modified dicyclopentadiene type epoxy acrylate having an acid value of the solid content of 100 mgKOH / g (corresponding to the component (A1-1); hereinafter referred to as "acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative 8").

[0146] <Synthesis Example 9> Synthesis of Acid-Modified Ethylenically Unsaturated Group-Containing Epoxy Derivative Containing No Alicyclic Skeleton 682 parts by mass of an oxazolidone ring-containing epoxy resin, 104 parts by mass of acrylic acid, 0.5 part by mass of methylhydroquinone, and 219 parts by mass of carbitol acetate were charged, heated to 90 °C, and reacted by stirring to dissolve the mixture. Next, the obtained solution was cooled to 60 °C, 4 parts by mass of triphenylphosphine was added, heated to 100 °C, and reacted until the acid value of the solution reached 1 mgKOH / g. Tetrahydrophthalic anhydride and carbitol acetate were added to the solution after the reaction, heated to 80 °C, reacted for about 6 hours, and then cooled to obtain an acid-modified ethylenically unsaturated group-containing epoxy acrylate having a solid content acid value of 80 mgKOH / g (corresponding to the component (A2-1); hereinafter referred to as "acid-modified ethylenically unsaturated group-containing epoxy derivative 9").

[0147] <Examples 4 to 8, Comparative Example 3> (Preparation of Photosensitive Resin Composition) The composition was formulated according to the formulation composition and formulation amounts shown in Table 2 and kneaded with a three-roll mill to prepare a photosensitive resin composition. In each example, propylene glycol monomethyl ether acetate was appropriately added to adjust the concentration, and a photosensitive resin composition having a solid content concentration of 50% by mass was obtained. (Preparation of Photosensitive Resin Film) A polyethylene terephthalate film with a thickness of 25 μm (G2-25, manufactured by Teijin Limited, trade name) was used as the carrier film. The photosensitive resin composition prepared in each example was applied onto the carrier film so that the film thickness after drying would be 25 μm, and then dried at 100 °C for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a biaxially stretched polypropylene film (MA-411, manufactured by Oji Eftex Inc., trade name) was laminated as a protective film onto the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, and a photosensitive resin film with the carrier film and the protective film laminated was produced. Using the produced photosensitive resin film, each evaluation was conducted according to the above method. The results are shown in Table 2.

[0148]

Table 2

[0149] Each component used in each example is as follows. (Component (A); · Epoxy derivative containing acid-modified ethylenically unsaturated group and alicyclic skeleton 4 [(Component (A1-1))]: The one obtained in Synthesis Example 4 was used. · Epoxy derivative containing acid-modified ethylenically unsaturated group and alicyclic skeleton 5 [(Component (A1-1))]: The one obtained in Synthesis Example 5 was used. · Epoxy derivative containing acid-modified ethylenically unsaturated group and alicyclic skeleton 6 [(Component (A1-1))]: The one obtained in Synthesis Example 6 was used. · Epoxy derivative containing acid-modified ethylenically unsaturated group and alicyclic skeleton 7 [(Component (A1-1))]: The one obtained in Synthesis Example 7 was used. · Epoxy derivative containing acid-modified ethylenically unsaturated group and alicyclic skeleton 8 [(Component (A1-1))]: The one obtained in Synthesis Example 8 was used. · Epoxy derivative containing acid-modified ethylenically unsaturated group 9 [(Component (A2-1))]: The one obtained in Synthesis Example 9 was used. · Dipentaerythritol pentaacrylate [(Component (Aiii))] (Component (B); · Photoinitiator 1: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, acetophenones · Photoinitiator 2: 2,4-diethylthioxanthone, thioxanthones (C) component; · Biphenyl type epoxy resin: "YX-4000" (manufactured by Mitsubishi Chemical Corporation, trade name) · o-Cresol novolak type epoxy resin: "EPICLON N-680" (manufactured by DIC Corporation, trade name) (F) component; · Silica: "SFP-20M" (manufactured by Denka Co., Ltd., average particle size 0.3 μm, trade name) (G) component; · Pigment: C.I.Pigment Blue 15 (phthalocyanine-based pigment, manufactured by Sanyo Color Works Co., Ltd., trade name) (H) component; · Hardener 1: Micronized melamine (manufactured by Nissan Chemical Industries, Ltd., trade name) · Hardener 2: 2-ethyl-4-methylimidazole

[0150] From Table 2, it can be seen that in Examples 4 to 8, the via resolution and crack resistance were excellent. On the other hand, in Comparative Example 3 where the (A1) component was not contained, the via resolution and crack resistance were insufficient.

Explanation of Symbols

[0151] 100A Multilayer printed wiring board 102 Circuit pattern 103 Interlayer insulating layer 104 Via (via hole) 105 Seed layer 106 Resist pattern 107 Copper circuit layer 108 Solder resist layer

Claims

1. A photosensitive resin composition for a multilayer printed wiring board, containing (A) a photopolymerizable compound having an ethylenically unsaturated group, (B) a photopolymerization initiator, (C) a thermosetting resin, and (F) an inorganic filler, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group includes (A1) a photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the ethylenically unsaturated group, the (A1) photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the ethylenically unsaturated group is a compound obtained by reacting (a1) an alicyclic skeleton-containing epoxy resin with (a2) an ethylenically unsaturated group-containing organic acid and then reacting the product with (a3) a polybasic acid anhydride containing a saturated group or an unsaturated group, which is (A1-1) an acid-modified ethylenically unsaturated group and alicyclic skeleton-containing epoxy derivative; the (a2) ethylenically unsaturated group-containing organic acid is at least one selected from the group consisting of acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid, and the (C) thermosetting resin includes a biphenyl-type epoxy resin. A photosensitive resin composition for a multilayer printed wiring board.

2. The photosensitive resin composition according to Claim 1, wherein the (A1) photopolymerizable compound having an acidic substituent and an alicyclic skeleton together with the ethylenically unsaturated group is represented by the following general formula (A-1). 【Chemical 1】 (In the 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. R Ａ２ represents an alkyl group having 1 to 12 carbon atoms. R 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. m １ is an integer of 0 to 6, m ２ is an integer of 0 to 3. n is 0 to 10.)

3. The photosensitive resin composition for a multilayer printed wiring board according to Claim 1 or 2, wherein the (A) photopolymerizable compound having an ethylenically unsaturated group further includes 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.

4. The photosensitive resin composition for a multilayer printed wiring board according to any one of Claims 1 to 3, wherein the content of the (C) thermosetting resin is 5 to 70% by mass based on the total solid content of the photosensitive resin composition.

5. The photosensitive resin composition for a multilayer printed wiring board according to any one of Claims 1 to 4, further containing (D) an elastomer.

6. The photosensitive resin composition for a multilayer printed wiring board according to claim 5, wherein the (D) elastomer contains at least one selected from the group consisting of a styrenic elastomer, an olefinic elastomer, a polyester elastomer, a urethane elastomer, a polyamide elastomer, an acrylic elastomer, and a silicone elastomer.

7. A photosensitive resin composition for a multilayer printed wiring board for forming a photo via, which is composed of the photosensitive resin composition for a multilayer printed wiring board according to any one of claims 1 to 6.

8. A photosensitive resin composition for a multilayer printed wiring board for an interlayer insulating layer, which is composed of the photosensitive resin composition for a multilayer printed wiring board according to any one of claims 1 to 6.

9. A photosensitive resin film for a multilayer printed wiring board, which is composed of the photosensitive resin composition for a multilayer printed wiring board according to any one of claims 1 to 6.

10. A photosensitive resin film for a multilayer printed wiring board for an interlayer insulating layer, which is composed of the photosensitive resin composition for a multilayer printed wiring board according to any one of claims 1 to 6.

11. A multilayer printed wiring board containing an interlayer insulating layer formed by using the photosensitive resin composition for a multilayer printed wiring board according to any one of claims 1 to 6.

12. A multilayer printed wiring board containing an interlayer insulating layer formed by using the photosensitive resin film for a multilayer printed wiring board according to claim 9.

13. A semiconductor package formed by mounting a semiconductor element on the multilayer printed wiring board according to claim 11 or 12.

14. A method for manufacturing a multilayer printed wiring board, comprising the following steps (1) to (4). Step (1): A step of laminating the photosensitive resin film for a multilayer printed wiring board according to claim 9 on 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 the step (1). Step (3): A step of roughening the vias and the interlayer insulating layer. Step (4): A step of forming a circuit pattern on the interlayer insulating layer.

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