JP7259286B2 - Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board - Google Patents

Description

The present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a multilayer printed wiring board, a semiconductor package, and a method for manufacturing a multilayer printed wiring board.

2. Description of the Related Art In recent years, as electronic devices have become smaller, lighter, and have more functions, the number of circuit layers in multilayer printed wiring boards has increased and wiring has become finer, resulting in higher densities. In particular, the density of semiconductor package substrates such as BGA (Ball Grid Array) and CSP (Chip Size Package) on which semiconductor chips are mounted has increased remarkably. There is a demand for further reduction in the diameter of vias (also referred to as "via holes").

As a method for manufacturing a printed wiring board, a method for manufacturing a multilayer printed wiring board by a build-up method (see, for example, Patent Document 1) in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated is mainly adopted. With the miniaturization of circuits, a semi-additive method, in which circuits are formed by plating, has become mainstream among methods of manufacturing multilayer printed wiring boards.
In the conventional semi-additive method, for example, (1) a thermosetting resin film is laminated on the conductor circuit, and the thermosetting resin film is cured by heating to form an "interlayer insulating layer", and (2) the following Then, vias for interlayer connection are formed by laser processing, desmearing and roughening are performed by alkaline permanganate treatment, etc. (3) After that, the substrate is subjected to electroless copper plating and patterned using a resist. After formation, electrolytic copper plating was performed to form a copper circuit layer, and (4) the resist was then removed and the electroless layer was flash-etched to form a copper circuit.

As described above, the conventional method of forming vias in an interlayer insulating layer formed by curing a thermosetting resin film mainly employs laser processing. However, as the size of via holes is becoming smaller, formation of via holes by laser irradiation using a laser processing machine has reached its limit. Furthermore, when forming vias with a laser processing machine, it is necessary to form each via hole one by one, and when a large number of vias must be formed due to the high density, it takes a lot of time to form the vias, and the manufacturing process is slow. There is a problem that the efficiency is degraded.

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

JP-A-7-304931 JP 2017-116652 A

The invention described in Patent Document 2 is a reduction in adhesive strength with plated copper caused by using a photosensitive resin composition instead of a conventional thermosetting resin composition as a material for an interlayer insulating layer or a surface protective layer. In addition, resolution of vias and adhesion to a substrate made of silicon material and chip parts were also set as problems, and these problems were solved. However, in addition to the miniaturization of wiring, the demand for resolution of vias and adhesion strength with plated copper is becoming stricter as insulating films become thinner and the diameter of via holes for interlayer connection becomes smaller. These performances have room for further improvement.
It is also conceivable to use a photosensitive resin composition or the like, which is a conventional solder resist material, as the material for the interlayer insulating layer. However, the interlayer insulation layer has characteristics that are not necessary for the solder resist, such as via resolution, adhesion strength with plated copper, insulation reliability between layers, and high heat resistance that can withstand repeated heating. Therefore, it is difficult to predict whether or not it can withstand practical use as an interlayer insulating layer, and it cannot be easily diverted.

The present invention has been made to solve the above-described problems, and provides a photosensitive resin composition excellent in via resolution and adhesive strength with plated copper, and a photosensitive resin composition for forming photovias. And it aims at providing the photosensitive resin composition for interlayer insulation layers. Further, the present invention provides a photosensitive resin film and a photosensitive resin film for an interlayer insulating layer comprising the photosensitive resin composition, provides a printed wiring board and a semiconductor package, and provides a method for manufacturing the printed wiring board. It is intended to

The present inventors have made intensive studies to solve the above problems, and as a result, have found that the problems can be solved by the following inventions. That is, the present invention provides the following photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing a multilayer printed wiring board.

1. (A) a photopolymerizable compound having an ethylenically unsaturated group and no isocyanuric skeleton, (B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton, and (C) a photopolymerization initiator containing, photosensitive resin composition.
2. (A) a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (A1) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and not having an isocyanuric skeleton The photosensitive resin composition according to 1 above, comprising:
3. 3. The photosensitive resin composition according to 1 or 2 above, wherein the (B) photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton comprises isocyanuric acid (meth)acrylate.
4. Any one of 1 to 3 above, wherein the (B) photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton contains at least one selected from isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate. 1. The photosensitive resin composition according to 1.
5. 5. The photosensitive resin composition as described in any one of 1 to 4 above, further comprising (D) a thermosetting resin.
6. 6. The photosensitive resin composition as described in any one of 1 to 5 above, further comprising (E) an elastomer.
7. 7. The photosensitive resin composition as described in any one of 1 to 6 above, further comprising (F) an inorganic filler.
8. In any one of 1 to 7 above, the content of the photopolymerizable compound (A) having an ethylenically unsaturated group and not having an isocyanuric skeleton is 5 to 60% by mass based on the total solid content. The photosensitive resin composition described.
9. 8. The content of the photopolymerizable compound (B) having an ethylenically unsaturated group and an isocyanuric skeleton is 0.5 to 15% by mass based on the total solid content, according to any one of 1 to 8 above. A photosensitive resin composition.
10. 10. The photosensitive resin composition as described in any one of 1 to 9 above, wherein the content of the photopolymerization initiator (C) is 0.1 to 15% by mass based on the total solid content.
11. 11. The photosensitive resin composition as described in any one of 1 to 10 above, which is used for forming photo vias.
12. 12. The photosensitive resin composition as described in any one of 1 to 11 above, which is used for forming an interlayer insulating layer.
13. 11. A photosensitive resin film comprising the photosensitive resin composition described in any one of 1 to 10 above.
14. 14. The photosensitive resin film as described in 13 above, which is used for forming an interlayer insulating layer.
15. 11. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of 1 to 10 above.
16. 14. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film described in 13 above.
17. 17. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to 15 or 16 above.
18. A method for producing a multilayer printed wiring board comprising the following steps (1) to (4) in order.
Step (1): A step of laminating the photosensitive resin film described in 13 above on one side or both sides of a circuit board.
Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1).
Step (3): a step of roughening the via and the interlayer insulating layer.
Step (4): forming a circuit pattern on the interlayer insulating layer.

According to the present invention, a photosensitive resin composition having excellent via resolution and adhesive strength with plated copper, a photosensitive resin film made of the photosensitive resin composition, the photosensitive resin composition or the photosensitive resin A multilayer printed wiring board using a film and a semiconductor package using the multilayer printed wiring board can be provided.
In addition, it is possible to provide a method for efficiently manufacturing a multilayer printed wiring board having vias of smaller diameter and higher resolution and having high adhesive strength between the interlayer insulating layer and the plated copper.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one aspect|mode of the manufacturing process of the multilayer printed wiring board which uses the hardened|cured material of the photosensitive resin composition of this embodiment as at least one of a surface protective film and an interlayer insulation film.

Hereinafter, a photosensitive resin composition according to one embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (A) a photopolymerizable compound having an ethylenically unsaturated group and no isocyanuric skeleton, and (B) a photopolymerized compound having an ethylenically unsaturated group and an isocyanuric skeleton. (C) a photopolymerization initiator.
In this specification, the above components may be referred to as component (A), component (B), component (C), etc., and other components may be abbreviated in the same manner. The "resin component" means the above-mentioned (A) component, (B) component, (C) component, etc., and does not contain the (F) inorganic filler described later. The non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition. liquid, starch syrup, and wax at room temperature.
In this specification, regarding the numerical range, the upper and lower limits of "to" are numerical values that can be arbitrarily combined, and it is also possible to use the numerical values shown in the examples as the upper and lower limits. . Regarding the content of each of the above components in the photosensitive resin composition, when there are multiple types of substances corresponding to each component, the total content of the substances is meant unless otherwise specified.

Since the photosensitive resin composition of the present embodiment is suitable for via formation by photolithography (also referred to as “photo via formation”), the present invention also provides a photosensitive resin composition for photo via formation. In addition, the photosensitive resin composition has excellent via resolution and adhesion strength with plated copper, and is suitable for forming an interlayer insulating layer of a multilayer printed wiring board. A flexible resin composition is also provided. In the present specification, the photosensitive resin composition includes a photosensitive resin composition for forming photovias and a photosensitive resin composition for interlayer insulating layers.
Each component that the photosensitive resin composition of the present embodiment may contain will be described in detail below.

<(A) Photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton>
The photosensitive resin composition of the present embodiment contains a photopolymerizable compound having an ethylenically unsaturated group and no isocyanuric skeleton as the component (A). Examples of ethylenically unsaturated groups possessed by component (A) include photopolymerized groups such as vinyl groups, allyl groups, propargyl groups, butenyl groups, ethynyl groups, phenylethynyl groups, maleimide groups, nadimide groups, and (meth)acryloyl groups. functional groups that exhibit Among these photopolymerizable functional groups, a (meth)acryloyl group is preferable from the viewpoint of improvement of via resolution and adhesion strength to plated copper.
Component (A) is a compound that exhibits photopolymerizability by having an ethylenically unsaturated group, and is a component that imparts photopolymerizability to the photosensitive resin composition of the present embodiment. Further, in the present embodiment, by using in combination with (B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton, which will be described later, particularly excellent adhesion strength to plated copper can be obtained. rice field.

As the photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (Ai) one polymerizable ethylenic A monofunctional vinyl monomer having an unsaturated group, (Aii) a difunctional vinyl monomer having two polymerizable ethylenically unsaturated groups and (Aiii) a multifunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups. An embodiment containing at least one selected from is preferred, and an embodiment containing the component (Aiii) is more preferred. Components (Ai) to (Aiii) preferably have a molecular weight of 1,000 or less.

((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. The (meth)acrylic acid alkyl esters include, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth) acrylic acid hydroxyl ethyl ester and the like. (Ai) A component may be used individually or in combination of multiple types.

((Aii) bifunctional vinyl monomer)
Examples of the difunctional 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. (Aii) A component may be used individually or in combination of multiple types.

((Aiii) polyfunctional vinyl monomer)
Examples of the polyfunctional vinyl monomer having at least three polymerizable ethylenically unsaturated groups include (meth)acrylate compounds having a trimethylolpropane-derived skeleton such as trimethylolpropane tri(meth)acrylate; tetramethylolmethane; (Meth)acrylate compounds having a tetramethylolmethane-derived skeleton such as tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate; Pentaerythritol-derived compounds such as pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate (Meth) acrylate compounds having a skeleton of; Dipentaerythritol penta (meth) acrylate, (meth) acrylate compounds having a skeleton derived from dipentaerythritol such as dipentaerythritol hexa (meth) acrylate; Ditrimethylolpropane tetra (meth) Examples thereof include (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane such as acrylate; and (meth)acrylate compounds having a skeleton derived from diglycerin.
Among these, a (meth)acrylate compound having a skeleton derived from dipentaerythritol is preferred, and dipentaerythritol penta(meth)acrylate is more preferred, from the viewpoint of improving via resolution and adhesion strength to plated copper. (Aiii) A component may be used individually or in combination of multiple types.
Here, the "(meth)acrylate compound having a skeleton derived from" (where "~" is the name of the compound) means an esterified product of the compound "~" and (meth)acrylic acid. , The esterified product also includes a compound modified with an alkyleneoxy group.

((A1) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and having no isocyanuric skeleton)
A photopolymerizable compound having an ethylenically unsaturated group enables alkali development and improves the resolution of vias and the adhesion strength to plated copper. Also preferred is an aspect containing a photopolymerizable compound that has a and does not have an isocyanuric skeleton. Here, examples of the acidic substituent include a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, and the like. Among them, a carboxyl group is preferred.
Component (A1) is a compound obtained by modifying (a1) an epoxy resin with (a2) a vinyl group-containing organic acid from the viewpoint of enabling alkali development and improving the resolution of vias and the adhesion strength to plated copper. (hereinafter sometimes referred to as "(A') component") is reacted with (a3) saturated or unsaturated group-containing polybasic acid anhydride (A1-1) acid-modified vinyl group-containing Epoxy resin derivatives can be used.

-(a1) epoxy resin-
The epoxy resin (a1) 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, and the like. Among these, glycidyl ether type epoxy resins are preferable from the viewpoint of enabling alkali development and improving via resolution and adhesion strength to plated copper.

Epoxy resins are also classified into various epoxy resins depending on the difference in the main skeleton, and each type of epoxy resin is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; ; novolak type epoxy resins other than the above bisphenol novolak type epoxy resins, such as phenol novolak type epoxy resins, cresol novolak type epoxy resins, biphenyl novolak type epoxy resins; phenol aralkyl type epoxy resins; biphenyl aralkyl type epoxy resins; stilbene type epoxy Resin; dicyclopentadiene type epoxy resin; naphthalene skeleton-containing type epoxy resin such as naphthalene type epoxy resin, naphthol novolak type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthylene ether type epoxy resin; biphenyl type epoxy resin biphenylaralkyl type epoxy resins; xylylene type epoxy resins; dihydroanthracene type epoxy resins; dicyclopentadiene type epoxy resins; alicyclic epoxy resins;
Among these, the epoxy resin (a1) is preferably a bisphenol-based novolac-type epoxy resin, and a bisphenol-F novolac-type epoxy resin, from the viewpoint of enabling alkali development and improving the resolution of vias and the adhesive strength with plated copper. Epoxy resins are more preferred. In addition, (a1) the epoxy resin may be used alone or in combination.

More specifically, the (a1) epoxy resin is preferably an epoxy resin having a structural unit represented by the following general formula (1).

In general formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and each Y ¹¹ independently represents a hydrogen atom or a glycidyl group. A plurality of R ¹¹ may be the same or different. At least one of the plurality of Y ¹¹ represents a glycidyl group.
From the viewpoint of via resolution and adhesion strength to plated copper, R ¹¹ is preferably a hydrogen atom. From the same point of view, Y ¹¹ is preferably a glycidyl group.
The number of structural units in the (a1) epoxy resin having a structural unit represented by the general formula (1) is 1 or more, preferably 10 to 100, more preferably 15 to 80, and further It is preferably 15-70. When the number of structural units is within the above range, adhesive strength, heat resistance and insulating properties tend to improve.
In the general formula (1), those in which both R ¹¹ are hydrogen atoms and both Y ¹¹ are glycidyl groups are referred to as EXA-7376 series (manufactured by DIC Corporation, trade name), and all R ¹¹ are Those having a methyl group and Y ¹¹ each having a glycidyl group are commercially available as EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).

-(a2) vinyl group-containing organic acid-
The (a2) vinyl group-containing organic acid is not particularly limited, but preferably includes, for example, a vinyl group-containing monocarboxylic acid. Examples of vinyl group-containing monocarboxylic acids include acrylic acid, dimers of acrylic acid, methacrylic acid, β-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, and the like. Acrylic acid derivative; half-ester compound which is a reaction product of hydroxyl group-containing (meth)acrylate and dibasic acid anhydride; reaction product of vinyl group-containing monoglycidyl ether or vinyl group-containing monoglycidyl ester and dibasic acid anhydride a half-ester compound;

The semi-ester compound can be obtained, for example, by reacting a hydroxyl group-containing (meth)acrylate, a vinyl group-containing monoglycidyl ether, or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. The component (a2) may be used alone or in combination.

Examples of hydroxyl group-containing (meth)acrylates, vinyl group-containing monoglycidyl ethers and vinyl group-containing monoglycidyl esters that can be used in synthesizing the half-ester compounds described above as examples of component (a2) include hydroxyethyl (meth) ) acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate , glycidyl (meth)acrylate and the like.

The dibasic acid anhydride used for synthesizing the above half-ester compound may contain a saturated group or may contain an unsaturated group. Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , ethylhexahydrophthalic anhydride, and itaconic anhydride.

In the reaction of the component (a1) and the component (a2), the reaction can be carried out at a ratio of 0.6 to 1.05 equivalents of the component (a2) with respect to 1 equivalent of the epoxy group of the component (a1). Preferably, they may be reacted at a ratio of 0.8 to 1.0 equivalents. By reacting in such a ratio, there is a tendency that the photopolymerizability is improved, that is, the photosensitivity is increased, and the via resolution is improved.

The above component (a1) and the above component (a2) can be reacted in an organic solvent. Examples of organic solvents include ketone-based organic solvents such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon-based organic solvents such as toluene, xylene, and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl; glycol ether-based organic solvents such as ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ester-based organic solvents such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; octane, aliphatic hydrocarbon-based organic solvents such as decane; and petroleum-based organic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

Furthermore, it is preferable to use a catalyst to promote the reaction between the component (a1) and the component (a2). Examples of catalysts include amine catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltrimethylammonium iodide; triphenylphosphine and the like. and phosphine catalysts. Among them, phosphine-based catalysts are preferred, and triphenylphosphine is more preferred.
The amount of the catalyst to be used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 100 parts by mass in total of the component (a1) and the component (a2). is 0.1 to 2 parts by mass. The amount used tends to accelerate the reaction between the component (a1) and the component (a2).

Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Polymerization inhibitors include, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol.
When a polymerization inhibitor is used, the amount used is preferably based on a total of 100 parts by mass of the component (a1) and the component (a2) from the viewpoint of improving the storage stability of the photosensitive resin composition. is 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.

The reaction temperature of the component (a1) and the component (a2) is preferably 60 to 150°C, more preferably 80 to 120°C, still more preferably 90 to 110°C, from the viewpoint of productivity.

The component (A′) obtained by reacting the component (a1) with the component (a2) is 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). It is inferred that it has a

-(a3) polybasic acid anhydride-
The component (a3) may contain a saturated group or may contain an unsaturated group. Examples of component (a3) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Examples include ethylhexahydrophthalic anhydride and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferable from the viewpoint of via resolution.

By further reacting the (A') component obtained above with the (a3) component containing a saturated or unsaturated group, the hydroxyl groups of the (A') component (the hydroxyl groups originally present in the (a1) component (A1-1) is a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and having no isocyanuric skeleton, in which the acid anhydride group of the component (a3) is semi-esterified. It is presumed that an acid-modified vinyl group-containing epoxy resin derivative is produced.

In the reaction between the component (A') and the component (a3), for example, 0.1 to 1.0 equivalents of the component (a3) are reacted with respect to 1 equivalent of hydroxyl groups in the component (A'). , (A1-1) the acid value of the acid-modified vinyl group-containing epoxy resin derivative can be adjusted.
(A1-1) The acid-modified vinyl group-containing epoxy resin derivative preferably has an acid value of 30 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, still more preferably 50 to 100 mgKOH/g. When the acid value is 30 mgKOH/g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution is improved, and when it is 150 mgKOH/g or less, the electrical properties of the cured film tend to be improved.

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

(A1-1) As the acid-modified vinyl group-containing epoxy resin derivative, a commercially available product may be used. 1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185, ZCR-1569H, ZXR-1807, ZCR-6000, ZCR-8000 (manufactured by Nippon Kayaku Co., Ltd., trade names), UE-9000 , UE-EXP-2810PM, and UE-EXP-3045 (manufactured by DIC Corporation, trade names).

As the component (A1), (A1-2) a styrene-maleic acid-based resin such as a hydroxyethyl (meth)acrylate-modified styrene-maleic anhydride copolymer can also be used. In this case, the component (A1-2) can be used together with the component (A1-1). The component (A1-2) may be used alone or in combination.

Further, as the component (A1), a compound obtained by modifying the (a1) epoxy resin with (a2) a vinyl group-containing organic acid, that is, the component (A') is reacted with an isocyanate compound (A1- 3) Epoxy polyurethane resin can also be used. Component (A1-3) may be used alone or in combination.

((A1) the molecular weight of the photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and not having an isocyanuric skeleton)
The weight average molecular weight (Mw) of component (A1) is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and even more preferably 5,000 to 18,000. Within this range, the resolution of vias and the adhesive strength with plated copper are improved. In particular, the weight-average molecular weight (Mw) of the acid-modified vinyl group-containing epoxy resin derivative (A1-1) is preferably within the above range. Here, in this specification, the weight average molecular weight is a value measured by the method described in Examples.

(Content of component (A))
The content of component (A) is not particularly limited, but from the viewpoints of via resolution and adhesion strength with plated copper, as well as heat resistance, electrical properties and chemical resistance, photosensitivity It is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, even more preferably 20 to 50% by mass, still more preferably 30 to 40% by mass, based on the total amount of resin components in the resin composition.

Although the component (A) is not particularly limited, it is possible to use the component (A1) and the component (Aiii) in combination from the viewpoint of improving the resolution of vias and the adhesive strength with plated copper. is preferred. In this case, the content ratio [(A1)/(Aiii)] (mass ratio) of the component (A1) and the component (Aiii) is preferably 2 to 20, more preferably 3 to 15, and even more preferably 4 to 12.

<(B) Photopolymerizable Compound Having Ethylenically Unsaturated Group and Isocyanuric Skeleton>
The photosensitive resin composition of this embodiment contains a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton as the component (B). If the component (B) is not included, particularly excellent adhesive strength with plated copper cannot be obtained. Examples of the ethylenically unsaturated group possessed by the photopolymerizable compound of component (B) include the same functional groups exhibiting photopolymerizability as the ethylenically unsaturated groups of component (A) above. (Meth)acryloyl group is preferred, and acryloyl group is more preferred, from the viewpoint of improving the resolution and adhesive strength with plated copper.

(B) The photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton can be used without particular limitation as long as it has these ethylenically unsaturated groups and an isocyanuric skeleton. ) Isocyanuric acid (meth)acrylates having an acryloyl group and an isocyanuric skeleton are preferred, isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate are more preferred, and isocyanuric acid diacrylate and isocyanuric acid triacrylate are further preferred. preferable.

Among these, EO-modified isocyanuric acid di(meth)acrylate, EO-modified isocyanuric acid tri(meth)acrylate, PO-modified isocyanuric acid di(meth)acrylate, and alkylene oxide groups introduced by alkylene oxide modification such as EO-modification and PO-modification. ) acrylate, PO-modified isocyanuric acid tri(meth)acrylate, EO/PO-modified isocyanuric acid di(meth)acrylate, EO/PO-modified isocyanuric acid tri(meth)acrylate and other alkylene oxide-modified isocyanuric acid (meth)acrylates, and these A caprolactone-modified product of; and isocyanuric acid monoallyl type epoxy di(meth)acrylate and the like are preferable. More specific examples include di(2-(meth)acryloyloxyethyl)isocyanurate, tri(2-(meth)acryloyloxyethyl)isocyanurate, alkylene oxide modified products thereof, caprolactone modified products, and the like. These isocyanuric acid (meth)acrylates can be used alone or in combination of multiple types.

(Content of component (B))
The content of component (B) is not particularly limited, but from the viewpoint of improving the resolution of vias and the adhesive strength with plated copper, based on the total amount of resin components in the photosensitive resin composition, preferably 0.1 to 20 mass %, more preferably 0.5 to 15 mass %, still more preferably 1 to 10 mass %, still more preferably 3 to 8 mass %.

<(C) Photoinitiator>
The photosensitive resin composition of the present embodiment contains (C) a photopolymerization initiator. (C) If the photopolymerization initiator is not included, excellent via resolution and adhesion strength to plated copper cannot be obtained. Component (C) is not particularly limited as long as it can polymerize component (A), and can be appropriately selected from commonly used photopolymerization initiators.

Examples of the photopolymerization initiator of component (C) include benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; -2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4 -(methylthio)phenyl]-2-morpholino-1-propanone, N,N-dimethylaminoacetophenone and other acetophenone-based photopolymerization initiators; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Anthraquinone-based photopolymerization initiators such as chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Photopolymerization initiator; ketal photopolymerization initiator such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, Michler's ketone, 4-benzoyl -benzophenone-based photopolymerization initiators such as 4'-methyldiphenyl sulfide; acridine-based photopolymerization initiators such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; Acylphosphine oxide photopolymerization initiators such as trimethylbenzoyldiphenylphosphine oxide; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl- 6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime), 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime] etc. and oxime ester photopolymerization initiators. Among these, acetophenone-based photopolymerization initiators and thioxanthone-based photopolymerization initiators are preferred, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone are preferred. more preferred.
Component (C) may be used alone or in combination of multiple types. When multiple types are used in combination, it is preferable to use an acetophenone-based photopolymerization initiator and a thioxanthone-based photopolymerization initiator in combination. -1-[4-(Methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone are more preferably used in combination.

(Content of component (C))
The content of component (C) is not particularly limited, but is preferably 0.1 to 15% by mass, more preferably 0.2 to 5% by mass, based on the total amount of resin components in the photosensitive resin composition. , more preferably 0.4 to 1.5% by mass. When the content of component (C) is 0.1% by mass or more, the risk of elution of the exposed portion during development in the interlayer insulating layer formed using the photosensitive resin composition is reduced. , 15% by mass or less, the heat resistance tends to be improved.

<(C') photopolymerization initiation aid>
The photosensitive resin composition of the present embodiment may contain (C') a photopolymerization initiation aid together with the above component (C). (C') Photopolymerization initiation aids include, for example, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, and the like. and a tertiary amine-based photopolymerization initiation aid. (C') A component may be used individually or in combination of multiple types.
When the photosensitive resin composition of the present embodiment contains component (C′), the content thereof is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.5% by mass, more preferably 0.05 to 0.3% by mass. In addition, the photosensitive resin composition of the present embodiment may not contain the component (C').

<(D) Thermosetting resin>
The photosensitive resin composition of the present embodiment can further contain (D) a thermosetting resin in addition to the above components (A) to (C). Including (D) a thermosetting resin improves heat resistance in addition to improving the resolution of vias and the strength of adhesion to plated copper.
Examples of thermosetting resins include epoxy resins, phenol resins, unsaturated imide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins. resins, triazine resins, melamine resins, and the like. Moreover, it is not particularly limited to these, and known thermosetting resins can be used. These thermosetting resins can be used alone or in combination of multiple types.
Among them, epoxy resin is preferable. Epoxy resins do not contain those corresponding to the above component (A), and in that respect, the epoxy resin used as (D) the thermosetting resin can be said to have no ethylenically unsaturated groups. In addition, a substance having an epoxy group while satisfying the above conditions is included in the component (D).

The epoxy resin of component (D) 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, and the like. Among these, glycidyl ether type epoxy resins are preferred.

Epoxy resins are also classified into various epoxy resins depending on the difference in the main skeleton, and each type of epoxy resin is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; novolak type epoxy resins other than the bisphenol novolac type epoxy resins, such as phenol novolak type epoxy resins, cresol novolak type epoxy resins, biphenyl novolak type epoxy resins; phenol aralkyl type epoxy resins; biphenyl aralkyl type epoxy resins; stilbene type epoxy Resin; dicyclopentadiene type epoxy resin; naphthalene skeleton-containing type epoxy resin such as naphthalene type epoxy resin, naphthol novolak type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, 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; Trimethylol-type epoxy resins; aliphatic chain epoxy resins; rubber-modified epoxy resins;

Among them, bisphenol-based epoxy resins, naphthol-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, and naphthylene ether-type epoxy resins are preferable from the viewpoint of improving adhesive strength with plated copper and further improving heat resistance. Bisphenol A type epoxy resin, bisphenol F type epoxy resin and biphenyl type epoxy resin are more preferable, bisphenol F type epoxy resin and biphenyl type epoxy resin are more preferable, and biphenyl type epoxy resin is still more preferable.

These epoxy resins can also use commercially available products. ”, “YL983U”), naphthalene-type epoxy resin (manufactured by DIC Corporation “HP4032D”, “HP4710”), naphthalene skeleton-containing polyfunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd. “NC7000”), naphthol-type epoxy resin (new Nippon Steel & Sumikin Co., Ltd. "ESN-475V"), epoxy resins having a biphenyl structure (Nippon Kayaku Co., Ltd. "NC3000H", "NC3500"), Mitsubishi Chemical Corporation "YX4000", "YX4000HK", "YL6121 ”), anthracene-type epoxy resin (manufactured by Mitsubishi Chemical Corporation “YX8800”), glycerol-type epoxy resin (manufactured by Nippon Steel & Sumitomo Metal Corporation “ZX1542”), naphthylene ether-type epoxy resin (manufactured by DIC Corporation “EXA7311-G4 ”) and the like.

(D) As the epoxy resin of the thermosetting resin, epoxy-modified polybutadiene can be used in addition to the resins exemplified above. As the epoxy resin of the component (D), it is preferable to use both an aromatic epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature. (Aromatic epoxy resin that is solid at room temperature) and epoxy-modified polybutadiene (epoxy resin that is liquid at room temperature) are preferably used in combination. In this case, the content ratio of both (aromatic epoxy resin that is solid at room temperature/epoxy resin that is liquid at room temperature) is preferably 100/5 to 60/40, more preferably 90/10, by mass. ~70/30.

The epoxy-modified polybutadiene preferably has hydroxyl groups at the molecular terminals, more preferably has hydroxyl groups at both molecular terminals, and further preferably has hydroxyl groups only at both molecular terminals. In addition, the number of hydroxyl groups possessed by the epoxy-modified polybutadiene is not particularly limited as long as it is one or more, preferably 1 to 5, more preferably 1 or 2, still more preferably 2.
The epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (2) from the viewpoint of adhesive strength with plated copper, heat resistance, thermal expansion coefficient and flexibility.

（上記一般式（２）中、ｎ_２１、ｎ_２２及びｎ_２３は各々、丸括弧内の構造単位の比率を表しており、ｎ_２１は０．０５～０．４０、ｎ_２２は０．０２～０．３０、ｎ_２３は０．３０～０．８０であり、さらに、ｎ_２１＋ｎ_２２＋ｎ_２３＝１．００、かつ（ｎ_２１＋ｎ_２３）＞ｎ_２２を満たす。ｙ_２１は、角括弧内の構造単位の数を表し、１０～２５０の整数である。）

(In the above general formula (2), n ₂₁ , n ₂₂ and n ₂₃ each represent the ratio of structural units in parentheses, n ₂₁ is 0.05 to 0.40, n ₂₂ is 0.02 ~ 0.30, n ₂₃ is 0.30 to 0.80, and satisfies n ₂₁ +n ₂₂ +n ₂₃ =1.00 and (n ₂₁ +n ₂₃ )>n _{22. y 21 is} square brackets represents the number of structural units within, and is an integer from 10 to 250.)

The bonding order of each structural unit in the general formula (2) is random. 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 interchanged, and each of (a), (b), and (c) and -[(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)-( Various bonding orders are possible, such as b)-(c)-]-, -[(c)-(b)-(c)]-[(b)-(a)-(a)-]-).
From the viewpoint of improving heat resistance, thermal expansion coefficient and flexibility in addition to the adhesive strength with plated copper, _n21 is preferably 0.10 to 0.30, and _n22 is preferably 0.10 to 0.30. , _n23 is preferably between 0.40 and 0.80. From the same point of view, _y21 is preferably an integer of 5-500.

Commercially available epoxidized polybutadiene having n ₂₁ =0.20, n ₂₂ =0.20, n ₂₃ =0.60, and y ₂₁ = integers of 10 to 250 in the general formula (2) include: Epolead (registered trademark) PB3600" (manufactured by Daicel Corporation) and the like.

(Content of component (D))
The content of component (D) is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5 to 40% by mass, based on the total amount of resin components in the photosensitive resin composition. , more preferably 7 to 30% by mass, particularly preferably 10 to 20% by mass. When the content of the component (D) is 5% by mass or more, sufficient cross-linking of the photosensitive resin composition is obtained, and the adhesive strength with the plated copper is improved. resolution tends to be good.

<(E) Elastomer>
The photosensitive resin composition of the present embodiment may further contain (E) an elastomer in addition to the above components (A) to (C). (E) By including an elastomer, the resolution of vias and the adhesive strength with plated copper are improved. In addition, the (E) component has the effect of suppressing a decrease in flexibility and adhesive strength with plated copper due to distortion (internal stress) inside the cured product due to cure shrinkage of the (A) component. .

Examples of elastomers include styrene-based elastomers, olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, etc. It is preferable to use at least one selected from these elastomers. . These elastomers consist of a hard segment component and a soft segment component, the former tending to contribute to heat resistance and strength, and the latter to flexibility and toughness.
Among the elastomers exemplified above, component (E) may be an olefin elastomer, a polyester elastomer, or It preferably contains at least one selected from urethane elastomers, and more preferably contains urethane elastomers. Further, it is more preferable that the component (E) is at least one selected from olefinic elastomers, polyester elastomers and urethane elastomers, and urethane elastomers are particularly preferable.

(styrene elastomer)
Styrenic elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and the like.

Commercially available styrene elastomers may be used, and examples of commercially available products include Tufprene, Solprene T, Asaprene T, and Tuftec (manufactured by Asahi Kasei Corporation, "Tufprene", "Asaprene" and "Tuftec" are Registered trademark), Elastomer AR (manufactured by Aron Kasei Co., Ltd.), Kraton G, Super Reflex (manufactured by Shell Japan Co., Ltd.), JSR-TR, TSR-SIS, Dynaron (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.), Lavalon (manufactured by Mitsubishi Chemical Corporation, "Lavalon" is a registered trademark) Trademarks), Septon, Hybler (all manufactured by Kuraray Co., Ltd., “Septon” and “Hibler” are registered trademarks), Sumiflex (manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (all manufactured by Riken Technos Co., Ltd., Rheostomer ” and “Actimer” are registered trademarks).

(Olefin elastomer)
Examples of olefinic elastomers include polymers or copolymers of α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. The olefinic elastomer may have a hydroxyl group at the molecular terminal, and preferably has a hydroxyl group at the molecular terminal.
Examples of olefinic elastomers include polyethylene, polybutadiene, hydroxyl-containing polybutadiene, hydroxyl-containing polyisopropyl, ethylene-propylene copolymer (EPR), and ethylene-propylene-diene copolymer (EPDM). Further, the α-olefin having 2 to 20 carbon atoms and a non-conjugated diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene and isoprene. A copolymer etc. are also mentioned. Carboxy-modified NBR obtained by copolymerizing a butadiene-acrylonitrile copolymer with methacrylic acid may also be used.
The olefinic elastomer preferably has a number average molecular weight of 1,000 to 5,000, more preferably 1,500 to 3,500.

As the olefinic elastomer, commercially available products may be used. Commercially available products include, for example, Milastoma (manufactured by Mitsui Chemicals, Inc., trade name), EXACT (manufactured by ExxonMobil, trade name), ENGAGE (The Dow Chemical Company, product name), Poly ip, Poly bd (Idemitsu Kosan Co., Ltd., product name), hydrogenated styrene-butadiene rubber “DYNABON HSBR” (JSR Corporation, product name), butadiene-acrylonitrile copolymer "NBR series" (manufactured by JSR Corporation, trade name), "XER series" of butadiene-acrylonitrile copolymer modified with carboxyl groups at both ends (manufactured by JSR Corporation, trade name), epoxidized polybutadiene partially epoxidized Examples include polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd., trade name), PB-4700, PB-3600 (manufactured by Daicel Corporation, trade name), and the like.

(polyester elastomer)
Polyester-based elastomers include those obtained by polycondensation of dicarboxylic acids or derivatives thereof and diol compounds or derivatives thereof.
Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalene dicarboxylic acid; 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. As the dicarboxylic acid, it is also preferable to use a dimer acid derived from a natural product, from the viewpoint of improving via resolution, adhesive strength with plated copper, and insulation reliability. A dicarboxylic acid may be used alone or in combination.
Specific examples of the diol compounds include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; - an alicyclic diol such as cyclohexanediol; A diol compound may be used alone or in combination.
The polyester elastomer preferably has a number average molecular weight of 900 to 30,000, more preferably 1,000 to 25,000, even more preferably 5,000 to 15,000.

Commercially available polyester elastomers may be used, and examples of commercially available products include Hytrel (manufactured by Toray DuPont Co., Ltd., "Hytrel" is a registered trademark), Pelprene (manufactured by Toyobo Co., Ltd., "Pelprene" is registered trademark), Espel (manufactured by Hitachi Chemical Co., Ltd., "Espel" is a registered trademark), and the like.

(urethane elastomer)
Examples of urethane-based elastomers include those containing a hard segment composed of a short-chain diol and diisocyanate and a soft segment composed of a high-molecular-weight (long-chain) diol and diisocyanate.
Polymeric (long-chain) diols include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-heptylene adipate), xylene carbonate), poly(1,6-hexylene-neopentylene adipate), and the like. The number average molecular weight of the high molecular weight (long chain) diol is preferably 500 to 10,000.
Short-chain diols include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like. The number average molecular weight of the short-chain diol is preferably 48-500.

As the urethane-based elastomer, commercial products may be used, and examples of commercial products include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), Miractran series (manufactured by Nippon Miractran Co., Ltd., "Miractran " is a registered trademark), Hitaroid series (manufactured by Hitachi Chemical Co., Ltd., "Hitaroid" is a registered trademark), and the like.

(polyamide elastomer)
Examples of polyamide-based elastomers include polyamide as a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, and polyacrylate. , polymethacrylate, polyurethane, silicone rubber, etc. as soft segment components.

Commercially available polyamide elastomers may be used, and examples of commercially available products include UBE polyamide elastomer (manufactured by Ube Industries, Ltd.), Daiamide (manufactured by Daicel-Evonik Co., Ltd., "Daiamide" is a registered trademark), and PEBAX. (manufactured by Toray Industries, Inc.), Grillon ELY (manufactured by M Chemie Japan Co., Ltd., "Grillon" is a registered trademark), Novamid (manufactured by Mitsubishi Chemical Corporation), Grelix (manufactured by Toyobo Co., Ltd., "Grelax" is a registered trademark) ) and the like.

(acrylic elastomer)
Examples of acrylic elastomers include polymers of raw material monomers containing acrylic acid ester as a main component. Suitable acrylic acid esters include ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like. Moreover, as a cross-linking monomer, those obtained by copolymerizing glycidyl methacrylate, allyl glycidyl ether, etc., and those obtained by copolymerizing acrylonitrile, ethylene, etc. may be used. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer and the like.

(silicone elastomer)
Silicone-based elastomers are elastomers containing organopolysiloxane as a main component, and are classified into, for example, polydimethylsiloxane-based elastomers, polymethylphenylsiloxane-based elastomers, polydiphenylsiloxane-based elastomers, and the like.

Commercially available silicone elastomers may be used, and examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series and SH series (manufactured by Dow Corning Toray Co., Ltd.). ).

(other elastomers)
In addition, as the component (E), polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyetheretherketone resin, polyetherimide resin, tetra An embodiment containing at least one selected from the group consisting of fluoroethylene resin, polyacrylonitrile resin, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxy-modified polyacrylonitrile is also preferred.

(Content of component (E))
The content of component (E) in the photosensitive resin composition of the present embodiment is preferably 2 to 30% by mass, more preferably 2 to 20% by mass, based on the total amount of resin components in the photosensitive resin composition. It is preferably 3 to 15% by mass, more preferably 3 to 10% by mass, and particularly preferably 5 to 10% by mass. When the content of component (E) is 2% by mass or more, the adhesive strength with plated copper is improved, and when it is 30% by mass or less, the resolution of vias and the adhesive strength with plated copper tend to be improved. become.

<(F) Inorganic filler>
The photosensitive resin composition of the present embodiment may contain (F) an inorganic filler. By containing (F) the inorganic filler, the resolution of the via is improved, and the reduction in thermal expansion is improved, thereby making it possible to further reduce the occurrence of warpage. Thermosetting resin compositions that have been conventionally used as interlayer insulating layers in multilayer printed wiring boards have been made to contain inorganic fillers to reduce thermal expansion. When included, the inorganic filler causes scattering of light and interferes with development, so it has been difficult to achieve low thermal expansion by including a large amount. As described above, there is a new problem unique to the photosensitive resin composition in containing an inorganic filler. Also, the resolution of the via is high. As a result, in this embodiment, by using (F) the inorganic filler, it is possible to achieve not only high resolution of vias but also low thermal expansion.

Component (F) includes, for example, silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), silicon nitride (Si ₃ N ₄ ), barium titanate (BaO.TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al(OH) ₃ ), magnesium hydroxide (Mg(OH) ₂ ), titanium lead oxide ( _PbO.TiO2 ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate ( _PLZT ), gallium oxide ( _Ga2O3 ), spinel ( _{MgO.Al2O3 )} , mullite (3Al _{2O3.2SiO2 )} , 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.TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C), and the like. (F) component can also be used individually or in combination of multiple types.

The average particle diameter of the inorganic filler (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, and even more preferably 0.1 to 2 μm, from the viewpoint of via resolution. In the present specification, the average particle size of the inorganic filler (B) is the average particle size of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. do.
First, after diluting (or dissolving) the photosensitive resin composition 1,000 times with methyl ethyl ketone, a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5) was used to measure the composition according to the international standard ISO 13321. , measure the particles dispersed in the solvent at a refractive index of 1.38, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is defined as the volume average particle diameter, which is the average of the inorganic filler. Particle size. In addition, the component (F) contained in the photosensitive resin film and the interlayer insulating layer provided on the carrier film was also diluted (or dissolved) to 1,000 times (volume ratio) using a solvent as described above. After that, it can be measured by using the submicron particle analyzer described above.

(Content of component (F))
The content of component (F) is not particularly limited, but from the viewpoint of improving via resolution, adhesion strength with plated copper, and insulation reliability, the total solid content of the photosensitive resin composition , preferably 5 to 80% by mass, more preferably 15 to 60% by mass, still more preferably 25 to 55% by mass.

<(G) Thermal polymerization initiator>
The photosensitive resin composition of the present embodiment can further contain (G) a thermal polymerization initiator in addition to the above components (A) to (C). (G) By containing a thermal polymerization initiator, the resolution of vias and the adhesive strength with plated copper are improved.
Examples of thermal polymerization initiators include, but are not limited to, diisopropylbenzene hydroperoxide "Percumyl P" (trade name, manufactured by NOF Corporation (hereinafter the same)), cumene hydroperoxide "Percumyl H". , Hydroperoxide-based thermal polymerization initiators such as t-butyl hydroperoxide "Perbutyl H"; ”, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane “Perhexa 25B”, t-butyl cumyl 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", etc. Initiators: ketone peroxide-based thermal polymerization initiators; peroxyketal-based thermal polymerization initiators such as n-butyl 4,4-di-(t-butylperoxy) valerate "Perhexa V"; diacyl peroxide-based thermal polymerization Initiators; peroxydicarbonate-based thermal polymerization initiators; organic peroxides such as peroxyester-based thermal polymerization initiators; pionitrile), azo compounds such as 2,2′-azobis(2,4-dimethylvaleronitrile); and the like. Among them, dialkylperoxaside-based thermal polymerization initiators are preferable from the viewpoint of not inhibiting photopolymerization and having a large effect of improving the physical properties and characteristics of the photosensitive resin composition. 5-bis(t-bitylperoxy)hexyne-3 is more preferred.
A thermal polymerization initiator may be used alone or in combination.

(Content of component (G))
When the photosensitive resin composition of the present embodiment contains component (G), its content is not particularly limited, but from the viewpoint of improving the resolution of vias and the adhesive strength with plated copper , preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, still more preferably 0.1 to 1% by mass, based on the total amount of resin components in the photosensitive resin composition.

<(H) pigment>
The photosensitive resin composition of the present embodiment may contain a pigment as the component (H) depending on the desired color in order to adjust the photosensitivity and improve the appearance by hiding the conductor pattern. As the component (H), a coloring agent that develops a desired color may be appropriately selected and used. and other known colorants are preferred.

(Content of component (H))
When the photosensitive resin composition of the present embodiment contains the component (H), the content is such that the solid content of the photosensitive resin composition makes it easy to identify the manufacturing apparatus and further conceals the conductor pattern. Based on the total amount, it is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, still more preferably 0.05 to 2% by mass.

<(I) Epoxy resin curing agent>
The photosensitive resin composition of the present embodiment may further contain (I) an epoxy resin curing agent for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the resulting insulating layer. good.
Specific examples of component (I) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5- Imidazole derivative-based epoxy resin curing agents such as hydroxymethylimidazole; guanamine-based epoxy resin curing agents such as acetoguanamine and benzoguanamine; polyamine-based epoxy resin curing agents such as melamine and polybasic hydrazides; organic acid salts and/or epoxy adducts thereof; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, Triazine derivative epoxy resin curing agents such as 2,4-diamino-6-xylyl-S-triazine; trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N- Tertiary amine-based epoxy resin curing agents such as methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine and m-aminophenol; polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak polyphenol-based epoxy resin curing agents such as; tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine and other organic phosphine-based epoxy resin curing agents; tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyl Phosphonium salt-based epoxy resin curing agents such as tributylphosnium chloride; quaternary ammonium salt-based epoxy resin curing agents such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydrides; diphenyliodonium tetrafluoroborate; triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate and the like.

(Content of component (I))
When the photosensitive resin composition of the present embodiment contains component (I), its content is preferably 0.01 to 20% by mass, more preferably 0, based on the total amount of resin components in the photosensitive resin composition. .1 to 10% by mass, more preferably 0.5 to 2% by mass.

<Diluent>
A diluent can be used for the photosensitive resin composition of this embodiment as needed. As a diluent, for example, an organic solvent or the like can be used. Examples of organic solvents include ketone-based organic solvents such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon-based organic solvents such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol monomethyl; Glycol ether organic solvents such as ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, carbitol acetate, etc. ester-based organic solvents; aliphatic hydrocarbon-based organic solvents such as octane and decane; and petroleum-based organic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. A diluent may be used alone or in combination.

(Content of diluent)
The content of the diluent is appropriately adjusted so that the concentration of the total solid content in the photosensitive resin composition is preferably 50 to 90% by mass, more preferably 60 to 80% by mass, and still more preferably 65 to 75% by mass. You can choose. By adjusting the usage amount of the diluent in this way, the applicability of the photosensitive resin composition is improved, and it becomes possible to easily form a higher-definition pattern.

<Other additives>
The photosensitive resin composition of the present embodiment may optionally contain polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol and pyrogallol; thickeners such as bentone and montmorillonite; silicone antifoaming agents; Defoaming agents such as fluorine-based defoaming agents and vinyl resin-based defoaming agents; silane coupling agents; Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, phosphate compounds of antimony compounds and phosphorus compounds, aromatic condensed phosphates, and halogen-containing condensed phosphates can be incorporated.

The photosensitive resin composition of the present embodiment can be obtained by kneading and mixing each component with a roll mill, bead mill, or the like.
Here, the photosensitive resin composition of this embodiment may be used in a liquid form or in a film form.
When used as a liquid, the method of applying the photosensitive resin composition of the present embodiment is not particularly limited. Various coating methods can be used. Among these methods, the printing method and the spin coating method may be appropriately selected from the viewpoint of easier formation of the photosensitive layer.
When used in the form of a film, for example, it can be used in the form of a photosensitive resin film, which will be described later. In this case, a photosensitive layer having a desired thickness is formed by laminating it on a carrier film using a laminator or the like. be able to. In addition, it is preferable to use it in the form of a film because the production efficiency of the multilayer printed wiring board is increased.

[Photosensitive resin film]
The photosensitive resin film of the present embodiment is made of the photosensitive resin composition of the present embodiment, and is suitable for forming, for example, a photosensitive layer serving as an interlayer insulating layer. The photosensitive resin film of the embodiment may be in a mode in which a 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 the multilayer printed wiring board, it is preferably 1 to 100 μm, more preferably 1 to 50 μm. , more preferably 5 to 40 μm.

For the photosensitive resin film of the present embodiment, for example, the photosensitive resin composition of the present embodiment is applied onto a carrier film by a known coating method such as a comma coater, bar coater, kiss coater, roll coater, gravure coater, and die coater. It can be obtained by forming a photosensitive layer that will later become an interlayer insulating layer by coating and drying with an apparatus.
Examples of carrier films include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film may be appropriately selected from the range of 5 to 100 μm, preferably 5 to 60 μm, more preferably 15 to 45 μm.

In addition, the photosensitive resin film of the present embodiment may be provided with a protective film on the surface of the photosensitive layer 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, the same polymer film as the carrier film described above may be used, or a different polymer film may be used.

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

The photosensitive resin film of the present embodiment is excellent in via resolution, adhesive strength with plated copper, and insulation reliability, and is therefore suitable as an interlayer insulating layer of a multilayer printed wiring board. That is, the photosensitive resin film of the present embodiment is suitable as a photosensitive resin film for interlayer insulation layers, which is suitably used for forming interlayer insulation layers. In addition, the photosensitive resin film for the interlayer insulating layer is generally called an interlayer insulating film in some cases.

[Multilayer printed wiring board and its manufacturing method]
The multilayer printed wiring board of the present embodiment includes an interlayer insulating layer formed using the photosensitive resin composition (the photosensitive resin film for interlayer insulating layer) of the present embodiment. The multilayer printed wiring board of the present embodiment is not particularly limited in its manufacturing method as long as it has a step of forming an interlayer insulating layer using the photosensitive resin composition of the present embodiment. It can be easily manufactured by the manufacturing method of the multilayer printed wiring board of the embodiment.

A method for producing a multilayer printed wiring board using the photosensitive resin film (interlayer insulating layer photosensitive resin film) of the present embodiment will be described with reference to FIG.
Multilayer printed wiring board 100A can be manufactured, for example, by a manufacturing method including the following steps (1) to (4).
Step (1): A step of laminating the photosensitive resin film of the present embodiment on one side or both sides of a circuit board (hereinafter also 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 also referred to as “laminating step (2)”). ).
Step (3): A step of roughening the via and the interlayer insulating layer (hereinafter also referred to as “roughening treatment step (3)”).
Step (4): forming a circuit pattern on the interlayer insulating layer (hereinafter also referred to as “circuit pattern forming step (4)”).

(Lamination step (1))
In the lamination step (1), for example, a vacuum laminator is used to laminate the photosensitive resin film (interlayer insulating layer photosensitive resin film) of the present embodiment on one or both sides of a circuit board (substrate 101 having a circuit pattern 102). It is a process to do. Vacuum applicator manufactured by Nichigo-Morton Co., Ltd., vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., roll type dry coater manufactured by Hitachi Ltd., vacuum laminator manufactured by Hitachi Chemical Electronics Co., Ltd., etc. mentioned.

When a protective film is provided on the photosensitive resin film, after peeling or removing the protective film, the photosensitive resin film is pressed against the circuit board while applying pressure and heat for lamination. can do.
The lamination is carried out, for example, by preheating the photosensitive resin film and the circuit board as necessary, and then applying pressure at a pressure of 70 to 130° C., a pressure of 0.1 to 1.0 MPa, and an air pressure of 20 mmHg (26.7 hPa) or less. Although it can be carried out under reduced pressure, it is not particularly limited to this condition. Moreover, the method of lamination may be a batch type or a continuous type using rolls.
Finally, the photosensitive resin film laminated on the circuit board (hereinafter sometimes referred to as a photosensitive layer) is cooled to around room temperature to form an interlayer insulating layer 103 . The carrier film may be peeled off now, or may be peeled off after exposure as described below.

(Photo via formation step (2))
In the photo-via forming step (2), at least part of the photosensitive resin film laminated on the circuit board is exposed and then developed. By exposure, the portion irradiated with the actinic rays is photocured to form a pattern. The exposure method is not particularly limited, and for example, a method of irradiating actinic rays imagewise through a negative or positive mask pattern called artwork (mask exposure method) may be employed, or LDI (Laser Direct Imaging). A direct drawing exposure method such as an exposure method or a DLP (Digital Light Processing) exposure method may be used to irradiate actinic rays in the form of an image.

A known light source can be used as a light source for actinic rays. Specific examples of light sources include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers that effectively emit ultraviolet or visible light. things; and the like. The amount of exposure ^is appropriately selected depending on the light source used and the thickness of the photosensitive layer. is preferred, and 15 to 500 J/m ² is more preferred.

In the development, the uncured portion of the photosensitive layer is removed from the substrate, thereby forming an interlayer insulating layer made of a photocured cured product on the substrate.
When a carrier film is present on the photosensitive layer, the carrier film is removed and then the unexposed portions are removed (developed). The developing method includes wet development and dry development, and either of them may be adopted. However, wet development is widely used, and wet development can be adopted in this embodiment as well.

In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include methods using a dipping method, a battle method, a spraying method, brushing, slapping, scraping, rocking immersion, and the like. Among them, 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 performed by one method, but two or more methods may be used in combination.
The composition of the developer may be appropriately selected according to the composition of the photosensitive resin composition. Examples thereof include alkaline aqueous solutions, water-based developers and organic solvent-based developers, among which alkaline aqueous solutions are preferred.

In the photovia formation step (2), after exposure and development, post UV curing with an exposure amount of about 0.2 to 10 J/cm ² (preferably 0.5 to 5 J/cm ² ) and about 60 to 250 ° C. An optional post thermal cure at a temperature of (preferably 120-200° C.) may and preferably does further cure the interlayer insulating layer.
As described above, an interlayer insulating layer having vias 104 is formed. There are no particular restrictions on the shape of the via, and examples of the cross-sectional shape include a square and an inverted trapezoid (the upper side is longer than the lower side). , squares, and the like. In the formation of vias by the photolithographic method in this embodiment, it is possible to form vias having an inverted trapezoidal cross-sectional shape (the upper side is longer than the lower side). preferred.

The size (diameter) of vias formed by this process can be less than 40 μm, and can be 35 μm or less or 30 μm or less, which is smaller than the size of vias produced by laser processing. can do. The lower limit of the size (diameter) of the via formed by this process is not particularly limited, but may be 15 μm or more, or may be 20 μm or more.
However, the size (diameter) of the via formed by this process is not limited to less than 40 μm, and may be, for example, about 200 μm or less.

(Roughening treatment step (3))
In the roughening treatment step (3), the surfaces of the vias and the interlayer insulating layer are roughened with a roughening liquid. In addition, when smear is generated in the photo-via forming step (2), the smear may be removed by the roughening liquid. Roughening treatment and smear removal can be performed at the same time.
Examples of the roughening liquid include a chromium/sulfuric acid roughening liquid, an alkaline permanganate roughening liquid (for example, a sodium permanganate roughening liquid), a sodium fluoride/chromium/sulfuric acid roughening liquid, and the like.
The roughening treatment forms uneven anchors on the surfaces of the vias and the interlayer insulating layer.

(Circuit pattern forming step (4))
A circuit pattern forming step (4) is a step of forming a circuit pattern on the interlayer insulating layer after the roughening treatment step (3).
From the viewpoint of fine wiring formation, the circuit pattern is preferably formed by a semi-additive process. Through the semi-additive process, the vias are made conductive as well as the circuit pattern is formed.

In the semi-additive process, the seed layer 105 is formed by electroless copper plating after using a palladium catalyst or the like on the entire surface of the via bottom, via wall surface and interlayer insulating layer after the roughening treatment step (3). to form The seed layer is for forming a power supply layer for 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, it tends to be possible to suppress the deterioration of connection reliability during electrolytic copper plating, and if it is 2.0 μm or less, the seed layer between wirings is flash etched. There is no need to increase the amount of etching during etching, and damage to wiring tends to be suppressed during etching.

The electroless copper plating treatment is carried out by depositing metallic copper on the surfaces of vias and interlayer insulating layers due to the reaction between copper ions and a reducing agent.
The electroless plating method and the electroplating method may be known methods and are not particularly limited, but the catalyst in the electroless plating step is preferably a palladium-tin mixed catalyst. The primary particle size is preferably 10 nm or less. Also, the plating composition in the electroless plating process preferably contains hypophosphorous acid as a reducing agent.
Commercially available products can be used as the electroless copper plating solution, and examples of commercially available products include "MSK-DK" manufactured by Atotech Japan Co., Ltd., and "Sulcup (registered trademark) PEA ver.4 manufactured by Uemura Kogyo Co., Ltd. ” and the like.

After applying 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 electrolytic copper plating, and from this point of view, the dry film resist with a thickness of 5 to 30 μm is preferable. As the dry film resist, the "Photech" series manufactured by Hitachi Chemical Co., Ltd., etc. are used.
After the dry film resist is thermally compressed, the dry film resist is exposed through a mask on which a desired wiring pattern is drawn, for example. The exposure can be performed with the same apparatus and light source as can be used when forming vias in the photosensitive resin film. After exposure, the carrier film on the dry film resist is peeled off, development is performed using an alkaline aqueous solution, and the unexposed portion is removed to form a resist pattern 106 . Thereafter, if necessary, an operation of removing development residues of the dry film resist using plasma or the like may be performed.
After development, copper electroplating is performed to form a copper circuit layer 107 and to fill vias.

After electrolytic copper plating, the dry film resist is stripped using an alkaline aqueous solution or an amine-based stripping agent. After stripping the dry film resist, the seed layer between the wirings is removed (flash etching). Flash etching is performed using acidic and oxidizing solutions such as sulfuric acid and hydrogen peroxide. Specific examples include "SAC" manufactured by JCU Corporation, "CPE-800" manufactured by Mitsubishi Gas Chemical Company, Inc., and the like. After the flash etching, if necessary, palladium or the like adhering to the portion between the wirings is removed. Palladium can be removed preferably using an acidic solution such as nitric acid or hydrochloric acid.

After stripping the dry film resist or after the flash etching step, post-baking is preferably performed. The post-baking treatment sufficiently heat-hardens the unreacted thermosetting components, thereby improving the adhesive strength with plated copper, insulation reliability, and hardening properties. Although the thermosetting conditions vary depending on the type of resin composition, etc., it is preferable that the curing temperature is 150 to 240° C. and the curing time is 15 to 100 minutes. The post-baking process completes a series of printed wiring board manufacturing processes by the photovia method, and this process is repeated according to the required number of interlayer insulating layers to manufacture boards. A solder resist layer 108 is preferably formed as the outermost layer.

[Semiconductor package]
The semiconductor package of this embodiment is obtained by mounting a conductive element on the multilayer printed wiring board of the above-described embodiment. In the semiconductor package of the present embodiment, for example, a semiconductor element such as a semiconductor chip or memory is mounted at a predetermined position on the multilayer printed wiring board of the present embodiment, and the semiconductor element is sealed with a sealing resin or the like. can be manufactured by

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.
The properties of the photosensitive resin composition obtained in each example were evaluated by the methods described below.

1. Evaluation of via resolution (1) Production of laminate for evaluation A printed wiring board substrate in which a 12 μm thick copper foil is laminated on a glass epoxy base material (manufactured by Hitachi Chemical Co., Ltd., trade name “MCL-E-679” ) is treated with a pre-roughening treatment liquid (manufactured by MEC Co., Ltd., trade name “CZ-8100”), washed with water and dried to obtain a pre-roughened printed wiring board substrate. rice field. Next, the protective film was peeled off from the carrier film and the photosensitive resin film with a protective film produced in each example and comparative example, and the exposed photosensitive resin film was treated with the pre-roughened printed wiring board substrate. After placing it so as to be in contact with the copper foil of , it was laminated using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., trade name "MVLP-500"). The conditions for lamination were a press hot plate temperature of 70° C., a vacuum drawing time of 20 seconds, a lamination pressing time of 30 seconds, an air pressure of 4 kPa or less, and a pressure of 0.4 MPa. After lamination, the laminate was left at room temperature for 1 hour or more to obtain a laminate for evaluation in which a photosensitive resin film and a carrier film were laminated in this order on the surface of the copper foil of the substrate for printed wiring board.
(2) Sensitivity measurement of photosensitive resin film After peeling and removing the carrier film of the laminate for evaluation obtained above, a 41-step tablet was placed, and a direct imaging exposure apparatus "DXP" using an ultra-high pressure mercury lamp as a light source was used. -3512" (manufactured by Oak Manufacturing Co., Ltd.). As the exposure pattern, a pattern in which dots with a diameter of φ30 to 100 μm are arranged in a grid pattern was used.
After the exposure, the photosensitive resin composition was allowed to stand at room temperature for 30 minutes, and the unexposed area of the photosensitive resin composition was developed by spraying for 60 seconds using a 1% by mass sodium carbonate aqueous solution at 30°C. The sensitivity of the photosensitive resin film (unit: mJ/cm ² ) was defined as the amount of exposure energy at which the gloss remaining step number of the 41-step tablet after development was 10.0. Using the pattern exposed at this sensitivity, the resolution of vias provided in the photosensitive resin film was evaluated according to the following evaluation criteria.
(3) Evaluation of Resolution Resolution was evaluated by exposing with an exposure energy amount such that the number of steps was 10.0, followed by spray development, and then observing the via pattern using an optical microscope. The openings of via portions of φ50 μm and φ60 μm of the dot pattern were evaluated according to the following criteria. The minimum diameter of the opening is 60 μm or less, that is, the determination of “A” and “B” indicates that the via has excellent resolution, and the minimum diameter of the opening is more than 60 μm or a cured film is obtained. If there was not, ie, the determination of "C" and "D", it is a failure.
A: The minimum diameter of the opening was 50 µm or less.
B: The minimum diameter of the opening was more than 50 μm and 60 μm or less.
C: The minimum diameter of the opening was over 60 µm.
D: A cured film was not obtained.

2. Evaluation of adhesive strength (peel strength) with plated copper (1) Production of laminate for evaluation and measurement of sensitivity of photosensitive resin film [1. Evaluation of resolution] In the procedures (1) and (2), the exposure machine used was a parallel light exposure machine using an ultra-high pressure mercury lamp as a light source (manufactured by Oak Manufacturing Co., Ltd., trade name "EXM-1201" ) above, except for changing to [1. Evaluation of Resolution] Perform the same operations as in the procedures (1) and (2) to determine the amount of exposure energy at which the number of remaining gloss steps is 10.0, which is the sensitivity of the photosensitive resin film (unit: mJ/cm ² ).
(2) Exposure step and development step Next, the carrier film of the evaluation laminate is peeled off, and the surface of the exposed photosensitive resin film is exposed to the entire surface with the exposure energy amount obtained above, and the photosensitive resin An insulating layer was formed by curing the film. After the exposure, the film was allowed to stand at room temperature for 30 minutes, and the unexposed area of the photosensitive resin film was developed by spraying a 1% by weight sodium carbonate aqueous solution at 30° C. for 60 seconds.
(3) Post-curing treatment Subsequently, post-UV curing is performed with a high-pressure mercury lamp irradiation type UV conveyor device (manufactured by Oak Manufacturing Co., Ltd.) at a conveyor speed where the exposure amount is 2 J / cm ² , and further hot air circulation type. Post heat curing was performed at 170° C. for 1 hour using a dryer (manufactured by Futaba Kagaku Co., Ltd.).
(4) Roughening treatment The laminate for evaluation after the post-curing treatment was treated at 70 ° C. for 5 minutes using a swelling liquid "Swelling Dip Securigant P", and then a roughening liquid "Dosing Securigant P500J". was used for 10 minutes at 70° C., and the neutralizing solution “Reduction Conditioner Securigant P500” was used for 5 minutes at 40° C. for roughening treatment. The swelling liquid, the roughening liquid and the neutralizing liquid were all manufactured by Atotech Japan Co., Ltd.
(5) Plating treatment The laminate for evaluation after the roughening treatment is subjected to electroless plating treatment at 30 ° C. for 20 minutes using an electroless plating solution "Prigant MSK-DK" (manufactured by Atotech Japan Co., Ltd.). Then, using an electroplating solution "Coparacid HL" (manufactured by Atotech Japan Co., Ltd.), electroplating is performed at 24 ° C. and 2 A / dm ² for 1 hour to form a plated copper layer on the insulating layer. Then, an evaluation substrate for measuring adhesive strength with plated copper was produced. The thickness of the plated copper formed by plating was set to 25 μm.
(6) Measurement of adhesive strength (peel strength) with plated copper The adhesive strength with plated copper was measured by measuring vertical peel strength at 23°C in accordance with JIS C6481 (1996). The adhesive strength with plated copper was evaluated according to the following criteria. If the adhesive strength with plated copper is 0.40 kN / m or more, it has excellent performance, that is, if it is judged as "A", it indicates that it has excellent adhesive strength with plated copper. , less than 0.40 kN/m, i.e., "B" and "C" judgments are unacceptable.
A: Adhesive strength with plated copper was 0.40 kN/m or more.
B: Adhesive strength to plated copper was less than 0.40 kN/m and 0.30 kN/m or more.
C: Adhesion strength with plated copper was less than 0.30 kN/m.

<Synthesis Example 1> (A1-1) Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Derivative 1 Bisphenol F novolac-type epoxy resin (in the above general formula (I), a structural unit in which Y ¹ is a glycidyl group and R ¹ is a hydrogen atom Bisphenol F novolak type epoxy resin containing (corresponding to component (a1)) 350 parts by mass, acrylic acid (corresponding to component (a2)) 70 parts by mass, methylhydroquinone 0.5 parts by mass, carbitol acetate 120 parts by mass After charging, the mixture was heated to 90° C. and stirred to cause a reaction to completely 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. 98 parts by mass of tetrahydrophthalic anhydride (corresponding to component (a3)) and 85 parts by mass of carbitol acetate were added to the solution after the reaction, heated to 80° C., and reacted for 6 hours.
After that, it was cooled to room temperature to obtain an acid-modified bisphenol F novolac type epoxy acrylate (corresponding to component (A1-1)) having a solid concentration of 73% by mass as acid-modified vinyl group-containing epoxy derivative 1.

<Method for measuring weight average molecular weight>
The weight-average molecular weight was measured using the following GPC measurement apparatus and measurement conditions, and the value converted using a standard polystyrene calibration curve was used as the weight-average molecular weight. In addition, a calibration curve was prepared using a set of 5 samples (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
(GPC measuring device)
GPC apparatus: High-speed GPC apparatus "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh stock Company made (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40°C
Flow rate: 0.35 ml/min Sample concentration: 10 mg/THF5 ml
Injection volume: 20 μl

<Synthesis Example 2> (A1-1) Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Derivative 2 320 parts by mass of cresol novolac type resin (EP4020G, manufactured by Asahi Organic Co., Ltd.), 925 parts by mass of epichlorohydrin, and 185 parts by mass of n-butanol and were dissolved in a flask equipped with a thermometer and stirrer. Thereafter, the temperature was raised to 65° C. while purging with nitrogen gas, and the pressure was reduced to an azeotropic pressure. During this time, the distillate azeotropically distilled was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the organic layer to the reaction system. Then, unreacted epichlorohydrin was distilled off under reduced pressure to obtain a crude epoxy resin. 1000 parts by mass of methyl isobutyl ketone and 100 parts by mass of n-butanol are added to the obtained crude epoxy resin and dissolved, and 20 parts by mass of a 10% by mass sodium hydroxide aqueous solution is added to the solution and reacted at 80° C. for 2 hours. After that, washing with 300 parts by mass of water was repeated three times, and it was confirmed that the pH of the washing liquid was neutral.
Next, the inside of the system was dehydrated by azeotropic distillation, and after passing through microfiltration, the solvent was distilled off under reduced pressure to obtain 350 parts by mass of a transparent liquid epoxy resin a-1. Subsequently, 70 parts by mass of acrylic acid (b), 0.5 parts by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged, heated to 90° C. and stirred to react to completely dissolve the mixture. The resulting 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. ) (c) 98 parts by mass and 850 parts by mass of carbitol acetate were added, heated to 80°C, and reacted for 6 hours. After that, the mixture was cooled to room temperature to obtain a THPAC-modified cresol novolak type epoxy acrylate epoxy resin having a solid content of 73% by mass as an acid-modified vinyl group-containing epoxy derivative 2 .

<Examples 1 to 5, Comparative Examples 1 and 2>
(Preparation of photosensitive resin composition)
A composition was blended according to the composition shown in Table 1 and kneaded in a three-roll mill to prepare a photosensitive resin composition. In each example, carbitol acetate was appropriately added to adjust the concentration to obtain a photosensitive resin composition having a solid concentration of 60% by mass.
(Preparation of photosensitive resin film)
A polyethylene terephthalate film (G2-16, manufactured by Teijin Limited, trade name) having a thickness of 25 μm was used as a carrier film, and the photosensitive resin composition prepared in each example was applied onto the carrier film so that the film thickness after drying was 25 μm. and 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 F-Tex Co., Ltd., trade name) is placed on the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film. A photosensitive resin film was produced by laminating a protective film, and laminating a carrier film and a protective film.
Each evaluation was performed according to the said method using the produced photosensitive resin film. Table 1 shows the evaluation results.

Each component used in each example is as follows.
Component (A): A photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton Acid-modified vinyl group-containing epoxy derivative 1: Obtained in Synthesis Example 1 above ((A1-1 ) component).
• Acid-modified vinyl group-containing epoxy derivative 2: obtained in Synthesis Example 2 above (corresponding to component (A1-1)).
- Polyfunctional vinyl monomer: dipentaerythritol pentaacrylate (corresponding to (Aiii) component)
Component (B): A photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton Isocyanurate acrylate 1: Tris (2-acryloyloxyethyl) isocyanurate (“FA-731A” (manufactured by Hitachi Chemical Co., Ltd.))
・ Isocyanurate acrylate 2: tris(2-acryloyloxyethyl) isocyanurate (“A-9300” (manufactured by Shin-Nakamura Chemical Co., Ltd.))
・ Isocyanuric acid acrylate 3: isocyanuric acid EO-modified di- and triacrylate (“Aronix M-315” (manufactured by Toagosei Co., Ltd.))
(C) Component: Photoinitiator/Photoinitiator 1: Acetophenone-based photoinitiator (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, "IRGACURE 907" (manufactured by BASF))
- Photopolymerization initiator 2: thioxanthone-based photopolymerization initiator (2,4-diethylthioxanthone, "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.))
(D) component: thermosetting resin/epoxy resin: biphenyl type epoxy resin (“YX-4000” (manufactured by Mitsubishi Chemical Corporation))
(E) Component: Elastomer Elastomer 1: Epoxidized polybutadiene ("PB-4700" (manufactured by Daicel Corporation))
・ Elastomer 2: Polyester resin (“Espel 1108” (manufactured by Hitachi Chemical Co., Ltd.))
(F) component: inorganic filler, silica: silica particles (average particle size: 1.3 μm, “CRS-2101-41” (manufactured by Tatsumori Co., Ltd.))

It was confirmed that the photosensitive resin composition of the present embodiment is excellent in via resolution and adhesion strength to plated copper. On the other hand, the resin composition of Comparative Example 1, which does not contain the component (B), is inferior in adhesion strength to the plated copper, and the resin composition of Comparative Example 2, which does not contain a photopolymerization initiator, has a via resolution and a All of the adhesive strengths with plated copper were inferior.

100A multilayer printed wiring board 101 substrate 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 (18)

(A) a photopolymerizable compound having an ethylenically unsaturated group and no isocyanuric skeleton, (B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton (however, an imide resin having a vinyl group ), (C) a photopolymerization initiator , (E) an elastomer (excluding acrylonitrile-butadiene rubber), and (F) an inorganic filler .
The photosensitive resin composition , wherein the content of the inorganic filler (F) is 25 to 80% by mass based on the total solid content . (A) a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (A1) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and not having an isocyanuric skeleton The photosensitive resin composition according to claim 1, comprising: 3. The photosensitive material according to claim 1 , wherein the photopolymerizable compound (B) having an ethylenically unsaturated group and an isocyanuric skeleton (excluding an imide resin having a vinyl group) contains isocyanuric acid (meth)acrylate. elastic resin composition. The (B) photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton (excluding an imide resin having a vinyl group) is selected from isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate. The photosensitive resin composition according to any one of claims 1 to 3, comprising at least one of 5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) a thermosetting resin. (E) Elastomer (excluding acrylonitrile-butadiene rubber) is one or more selected from the group consisting of styrene-based elastomers, polyester-based elastomers, urethane-based elastomers, and silicone-based elastomers. 1. The photosensitive resin composition according to claim 1. The photosensitive resin composition according to any one of claims 1 to 6, wherein the content of (E) elastomer (excluding acrylonitrile-butadiene rubber) is 2 to 30% by mass based on the total solid content. . Any one of claims 1 to 7, wherein the content of the photopolymerizable compound (A) having an ethylenically unsaturated group and not having an isocyanuric skeleton is 5 to 60% by mass based on the total solid content. The photosensitive resin composition according to Item 1. The content of the (B) photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton (excluding an imide resin having a vinyl group) is 0.5 to 15% by mass based on the total solid content. The photosensitive resin composition according to any one of claims 1 to 8. The photosensitive resin composition according to any one of claims 1 to 9, wherein the content of the photopolymerization initiator (C) is 0.1 to 15% by mass based on the total solid content. The photosensitive resin composition according to any one of claims 1 to 10, which is used for photovia formation. The photosensitive resin composition according to any one of claims 1 to 11, which is used for forming an interlayer insulating layer. A photosensitive resin film comprising the photosensitive resin composition according to any one of claims 1 to 10. 14. The photosensitive resin film according to claim 13, which is used for forming an interlayer insulating layer. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of claims 1 to 10. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to claim 13 . 17. A semiconductor package comprising a multilayer printed wiring board according to claim 15 or 16 and a semiconductor element mounted thereon. A method for producing a multilayer printed wiring board comprising the following steps (1) to (4) in order.
Step (1): A step of laminating the photosensitive resin film according to claim 13 on one side or both sides of a circuit board.
Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in step (1).
Step (3): a step of roughening the via and the interlayer insulating layer.
Step (4): forming a circuit pattern on the interlayer insulating layer.

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