JP2020086119A - Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package and method for manufacturing multilayer printed wiring board - Google Patents

Abstract

To provide a photosensitive resin composition excellent in resolution of a via and adhesive strength to plated copper, a photosensitive resin film made of the photosensitive resin composition, a multilayer printed wiring board using the photosensitive resin composition or the photosensitive resin film, and a semiconductor package using the multilayer printed wiring board.SOLUTION: The photosensitive resin composition comprises (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.SELECTED DRAWING: None

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 higher performance such as more multifunctional functions, multilayer printed wiring boards have been increased in density by increasing the number of circuit layers and miniaturizing wiring. Above all, the density of semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package), on which semiconductor chips are mounted, has been remarkably high. In addition to miniaturization of wiring, thinning of insulating film and interlayer connection are used. It is required to further reduce the diameter of the vias (also called “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 (for example, see Patent Document 1) in which an interlayer insulating layer and a conductor circuit layer are sequentially laminated is mainly adopted, In the manufacturing method of a multilayer printed wiring board, a semi-additive method in which a circuit is formed by plating has become mainstream as the circuit is miniaturized.
In the conventional semi-additive method, for example, (1) a thermosetting resin film is laminated on a conductor circuit, and the thermosetting resin film is cured by heating to form an “interlayer insulating layer”. Then, vias for interlayer connection are formed by laser processing, desmear treatment and roughening treatment are performed by alkaline permanganate treatment, etc. (3) After that, the substrate is subjected to electroless copper plating treatment, and a pattern is formed using a resist. After the formation, electrolytic copper plating is performed to form a copper circuit layer, and then (4) the resist is removed, and the electroless layer is flash-etched to form a copper circuit.

As described above, laser processing is mainly adopted as a method of forming vias in an interlayer insulating layer formed by curing a conventional thermosetting resin film. However, as miniaturization of via holes progresses, the formation of via holes by laser irradiation using a laser processing machine has reached a limit. Further, in forming a via by a laser processing machine, it is necessary to form each via hole one by one, and when it is necessary to provide a large number of vias due to high density, it takes a lot of time to form the via, The problem is that efficiency becomes poor.

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

Japanese Patent Laid-Open No. 7-304931 JP, 2017-116652, A

The invention described in Patent Document 2 reduces the adhesive strength with plated copper due to the use of a photosensitive resin composition instead of a conventional thermosetting resin composition as a material for an interlayer insulating layer or a surface protective layer. Is one of the problems, and further, the resolution of vias and the adhesion to the substrate of silicon material and the chip component are also problems, and these are solved. However, in addition to the miniaturization of wiring, thinning of the insulating film and the downsizing of via holes for interlayer connection are progressing, the required performance for the resolution of the via and the adhesive strength with the plated copper is becoming more severe, There is room for further improvement in these performances.
It is also conceivable to use a conventional photosensitive resin composition, which is a material for a solder resist, as the material for the interlayer insulating layer. However, the interlayer insulating layer has properties that were not required for the solder resist, such as resolution of vias, adhesive strength with plated copper, insulation reliability between layers, and high heat resistance that can withstand multiple heating. Since it is required, it is difficult to predict whether or not it can be practically used as an interlayer insulating layer, and it cannot be easily diverted.

The present invention has been made to solve the above problems, and is a photosensitive resin composition having excellent resolution of vias and adhesive strength with plated copper, and a photosensitive resin composition for photovia formation. And to provide a photosensitive resin composition for an interlayer insulating layer. Further, it provides a photosensitive resin film comprising the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer, a printed wiring board and a semiconductor package, and a method for producing the printed wiring board. The purpose is that.

The present inventors have conducted intensive studies to solve the above problems, and as a result, found that the following inventions can solve the problems. That is, the present invention provides the following photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for manufacturing 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 A photosensitive resin composition containing.
2. (A) a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (A1) a photopolymerizable compound having an acidic substituent together with an ethylenically unsaturated group, and having no isocyanuric skeleton The photosensitive resin composition according to 1 above, which comprises:
3. 3. The photosensitive resin composition according to 1 or 2 above, wherein the photopolymerizable compound (B) having an ethylenically unsaturated group and an isocyanuric skeleton contains isocyanuric acid (meth)acrylate.
4. Any of the above 1 to 3, wherein the photopolymerizable compound (B) 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. 2. The photosensitive resin composition according to item 1.
5. Furthermore, the photosensitive resin composition according to any one of 1 to 4 above, which further comprises (D) a thermosetting resin.
6. Furthermore, the photosensitive resin composition according to any one of 1 to 5 above, which further comprises (E) an elastomer.
7. Further, the photosensitive resin composition according to any one of 1 to 6 above, which further comprises (F) an inorganic filler.
8. The content of the photopolymerizable compound (A) having an ethylenically unsaturated group and not having an isocyanuric skeleton is 5 to 60% by mass on the basis of the total solid content, and any one of the above 1 to 7 The photosensitive resin composition described.
9. The content of the photopolymerizable compound having the (B) ethylenically unsaturated group and an isocyanuric skeleton is 0.5 to 15 mass% based on the total solid content, and the content is 1 to 8. Photosensitive resin composition.
10. The photosensitive resin composition according to any one of 1 to 9 above, wherein the content of the (C) photopolymerization initiator is 0.1 to 15% by mass based on the total solid content.
11. 11. The photosensitive resin composition according to any one of 1 to 10 above, which is used for forming a photo via.
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. A photosensitive resin film comprising the photosensitive resin composition according to 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. 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. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film as described in 13 above.
17. 17. A semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board according to 15 or 16 above.
18. The manufacturing method of the multilayer printed wiring board which has the following processes (1)-(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 a via by exposing and developing the photosensitive resin film laminated in the 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 excellent in resolution of vias and adhesion strength to plated copper, a photosensitive resin film comprising 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.
Further, it is possible to provide a method for efficiently manufacturing a multilayer printed wiring board having a via having a smaller diameter and a higher resolution and having a high adhesive strength between an interlayer insulating layer and plated copper.

It is a schematic diagram which shows one aspect 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 protection film and an interlayer insulation film.

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

[Photosensitive resin composition]
The photosensitive resin composition according to the present embodiment includes (A) a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, and (B) a photopolymerization having an ethylenically unsaturated group and an isocyanuric skeleton. A resin composition containing a polymerizable compound and (C) a photopolymerization initiator.
In the present specification, each of the above components may be referred to as a component (A), a component (B), a component (C), etc., and other components may be abbreviated in the same manner. The “resin component” is the above-mentioned component (A), component (B), component (C), etc., and means that the below-mentioned (F) inorganic filler is not included, and “solid content” means It is a non-volatile component excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and indicates a component that remains without volatilizing when the resin composition is dried, and is around 25° C. It also includes liquids, starch syrups and waxes at room temperature.
In the present specification, regarding the numerical range, the upper and lower limits of “to” are numbers that can be arbitrarily combined, and it is also possible to use the numbers shown in the examples as the upper and lower limits. .. Regarding the content of each component in the photosensitive resin composition, when there are plural kinds of substances corresponding to each component, unless otherwise specified, the content means the total content of the substances.

Since the photosensitive resin composition of the present embodiment is suitable for via formation by photolithography (also referred to as “photovia formation”), the present invention also provides a photosensitive resin composition for photovia formation. Further, since the photosensitive resin composition is excellent in resolution of vias and adhesive strength with plated copper, and is suitable for forming an interlayer insulating layer of a multilayer printed wiring board, the present invention provides a photosensitive resin for an interlayer insulating layer. Resin compositions are also provided. In the present specification, the term "photosensitive resin composition" includes a photosensitive resin composition for forming a photo via and a photosensitive resin composition for an interlayer insulating layer.
Hereinafter, each component that may be contained in the photosensitive resin composition of the present embodiment will be described in detail.

<(A) Photopolymerizable compound having ethylenically unsaturated group and not having isocyanuric skeleton>
The photosensitive resin composition of the present embodiment contains, as the component (A), a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton. Examples of the ethylenically unsaturated group contained in the component (A) include photopolymerization of vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth)acryloyl group, etc. And a functional group exhibiting properties. Among these functional groups exhibiting photopolymerizability, a (meth)acryloyl group is preferable from the viewpoint of improving the resolution of vias and the adhesive strength with plated copper.
The 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. In addition, in the present embodiment, particularly excellent adhesive strength with plated copper is obtained by using (B) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric skeleton, which will be described later. It was

As the photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (Ai) one polymerizable ethylenic compound is used from the viewpoint of improving the resolution of vias and the adhesion strength with plated copper. Monofunctional vinyl monomers having unsaturated groups, (Aii) bifunctional vinyl monomers having two polymerizable ethylenically unsaturated groups, and (Aiii) polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups. The embodiment containing at least one selected from the above is preferable, and the embodiment containing the component (Aiii) is more preferable. The 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 ester. Examples of the (meth)acrylic acid alkyl ester include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth) Acrylic acid hydroxyl ethyl ester and the like can be mentioned. The component (Ai) may be used alone or in combination of two or more kinds.

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

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

((A1) Photopolymerizable compound having an acidic substituent together with an ethylenically unsaturated group and having no isocyanuric skeleton)
The photopolymerizable compound having an ethylenically unsaturated group is (A1) an ethylenically unsaturated group and an acidic substituent in order to enable alkali development and to improve the resolution of vias and the adhesion strength with plated copper. And a photopolymerizable compound having no isocyanuric skeleton is also preferable. Here, examples of the acidic substituent include a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, and the like, which enables alkali development, and from the viewpoint of improving the resolution of vias and the adhesive strength with plated copper, Of these, a carboxyl group is preferable.
As the component (A1), a compound obtained by modifying the epoxy resin (a1) with a vinyl group-containing organic acid (a1) from the viewpoint of enabling alkali development and improving the resolution of vias and the adhesion strength with plated copper. (Hereinafter, it may be referred to as “(A′) component”.) (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 (a1) epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and the like. Among these, a glycidyl ether type epoxy resin is preferable from the viewpoint of enabling alkali development and improving the resolution of vias and the adhesion strength with plated copper.

Epoxy resins are also classified into various epoxy resins depending on the difference in the main skeleton, and further classified into the epoxy resins of the respective types described above. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin or other bisphenol type epoxy resin; bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or other bisphenol type novolac type epoxy resin A novolak type epoxy resin other than the above bisphenol type novolak type epoxy resin, such as a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a biphenyl novolak type epoxy resin; a phenol aralkyl type epoxy resin; a biphenyl aralkyl type epoxy resin; Resin; dicyclopentadiene type epoxy resin; naphthalene type epoxy resin, naphthol novolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthylene ether type epoxy resin and other naphthalene skeleton 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; aliphatic chain epoxy resin; rubber modified epoxy resin and the like.
Among these, as the (a1) epoxy resin, a bisphenol-based novolac-type epoxy resin is preferable, and a bisphenol-F novolac-type epoxy resin is preferable from the viewpoints of enabling alkali development and improving the resolution of vias and the adhesive strength with plated copper. Epoxy resins are more preferred. The epoxy resin (a1) may be used alone or in combination of two or more kinds.

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

In formula (1), R ¹¹ represents a hydrogen atom or a methyl group, and 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 the resolution of vias and the adhesive strength with plated copper, R ¹¹ is preferably a hydrogen atom. From the same viewpoint, Y ¹¹ is preferably a glycidyl group.
The number of structural units of the structural unit in the (a1) epoxy resin having the 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 to 70. When the number of structural units is within the above range, the adhesive strength, heat resistance and insulating property tend to be improved.
In the general formula (1), R ¹¹ is a hydrogen atom and Y ¹¹ is a glycidyl group, as EXA-7376 series (manufactured by DIC Corporation, trade name), and R ¹¹ is both A methyl group in which Y ¹¹ is a glycidyl group is commercially available as EPON SU8 series (trade name, manufactured by Mitsubishi Chemical Corporation).

-(A2) Vinyl group-containing organic acid-
The vinyl group-containing organic acid (a2) is not particularly limited, but for example, a vinyl group-containing monocarboxylic acid is preferable. As the vinyl group-containing monocarboxylic acid, for example, acrylic acid, a dimer of acrylic acid, methacrylic acid, β-furfuryl acrylic acid, β-styryl acrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, etc. Acrylic acid derivative; Half-ester compound which is a reaction product of hydroxyl group-containing (meth)acrylate and dibasic acid anhydride; Reaction formation of vinyl group-containing monoglycidyl ether or vinyl group-containing monoglycidyl ester and dibasic acid anhydride Half ester compound which is a product; and the like.

The above-mentioned half-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 of two or more kinds.

Examples of the hydroxyl group-containing (meth)acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester that can be used in the synthesis of the above-mentioned half-ester compound exemplified as the 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 in the synthesis of the above-mentioned half-ester compound may be one containing a saturated group or one containing an unsaturated group. Examples of the dibasic acid anhydride include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. , Ethylhexahydrophthalic anhydride, itaconic anhydride and the like.

In the reaction between the component (a1) and the component (a2), the component (a2) may be reacted at a ratio of 0.6 to 1.05 equivalents relative to 1 equivalent of the epoxy group of the component (a1). The reaction may be carried out at a ratio of preferably 0.8 to 1.0 equivalent. By reacting in such a ratio, the photopolymerization property is improved, that is, the photosensitivity is increased and the resolution of the via tends to be improved.

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

Further, it is preferable to use a catalyst in order to promote the reaction between the component (a1) and the component (a2). Examples of the catalyst include amine-based 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 the phosphine-based catalysts. Of these, phosphine catalysts are preferable, and triphenylphosphine is more preferable.
The amount of the catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 100 parts by mass of the component (a1) and the component (a2). Is 0.1 to 2 parts by mass. With the above-mentioned use amount, the reaction between the component (a1) and the component (a2) tends to be promoted.

A polymerization inhibitor is preferably used for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
When the polymerization inhibitor is used, its amount is preferably 100 parts by mass of the total 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, still more preferably 0.05 to 0.5 part by mass.

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

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 become.

-(A3) polybasic acid anhydride-
The component (a3) may contain a saturated group or may contain an unsaturated group. Examples of the component (a3) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Examples thereof include ethylhexahydrophthalic anhydride and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferable from the viewpoint of resolution of vias.

By further reacting the component (A′) obtained above with the component (a3) having a saturated or unsaturated group, the hydroxyl group of the component (A′) (the hydroxyl group originally present in the component (a1) is also included. And (a3) the acid anhydride group of component (a3) are half-esterified, have an ethylenically unsaturated group and an acidic substituent, and do not have an isocyanuric skeleton (A1-1). 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, by reacting the component (a3) in an amount of 0.1 to 1.0 equivalent with respect to 1 equivalent of the hydroxyl group in the component (A′). The acid value of the (A1-1) acid-modified vinyl group-containing epoxy resin derivative can be adjusted.
The acid value of the (A1-1) acid-modified vinyl group-containing epoxy resin derivative is preferably 30 to 150 mgKOH/g, more preferably 40 to 120 mgKOH/g, and further 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 further preferably 70 to 100° C.

As the (A1-1) acid-modified vinyl group-containing epoxy resin derivative, a commercially available product may be used, and examples of the commercially available product include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050 and TCR-. 1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185, ZCR-1569H, ZXR-1807, ZCR-6000, ZCR-8000 (above, Nippon Kayaku Co., Ltd., trade name), UE-9000. , UE-EXP-2810PM, UE-EXP-3045 (above, manufactured by DIC Corporation, trade name) and the like.

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

The component (A1) is obtained by reacting the compound (a1) obtained by modifying the epoxy resin (a1) with a vinyl group-containing organic acid (a2), that is, a component (A′) and an isocyanate compound (A1- 3) Epoxy polyurethane resin can also be used. The component (A1-3) may be used alone or in combination of two or more.

((A1) Molecular Weight of Photopolymerizable Compound Having Acid Substituent with Ethylenically Unsaturated Group and No Isocyanuric Skeleton)
The weight average molecular weight (Mw) of the component (A1) is preferably 3,000 to 30,000, more preferably 4,000 to 25,000, and further preferably 5,000 to 18,000. Within this range, the resolution of the via and the adhesive strength with the plated copper are improved. In particular, the weight average molecular weight (Mw) of the (A1-1) acid-modified vinyl group-containing epoxy resin derivative is preferably within the above range. Here, in the present specification, the weight average molecular weight is a value measured by the method described in Examples.

(Content of component (A))
The content of the component (A) is not particularly limited, but from the viewpoint of improving the resolution of the via and the adhesive strength with the plated copper, and further, heat resistance, electric characteristics and chemical resistance, It is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, still more preferably 20 to 50% by mass, and still more preferably 30 to 40% by mass, based on the total amount of the resin components of the resin composition.

The component (A) is not particularly limited, but the component (A1) and the component (Aiii) are used in combination from the viewpoint of improving the resolution of the via and the adhesion strength with the 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 further preferably 4 to. Twelve.

<(B) Photopolymerizable compound having ethylenically unsaturated group and isocyanuric skeleton>
The photosensitive resin composition of the present 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 contained in the photopolymerizable compound as the component (B) include the same functional groups exhibiting photopolymerizability as the ethylenically unsaturated group as the component (A). From the viewpoint of improving the resolution and improving the adhesive strength with plated copper, a (meth)acryloyl group is preferable, and an acryloyl group is more preferable.

As the photopolymerizable compound (B) having an ethylenically unsaturated group and an isocyanuric skeleton, those having an ethylenically unsaturated group and an isocyanuric skeleton can be used without particular limitation, and examples thereof include (meta ) Isocyanuric acid (meth)acrylate having an acryloyl group and an isocyanuric skeleton is preferably mentioned, isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate are more preferable, and isocyanuric acid diacrylate and isocyanuric acid triacrylate are more preferable. preferable.

Among these, EO-modified isocyanuric acid di(meth)acrylate, EO-modified isocyanuric acid tri(meth)acrylate, PO-modified isocyanuric acid di(meta) in which an alkylene oxide group is introduced by alkylene oxide modification such as EO modification or PO modification. ) Acrylate, alkylene oxide-modified isocyanuric acid (meth)acrylate such as 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 the like Preferred are caprolactone-modified products thereof; and isocyanuric acid monoallyl type epoxy di(meth)acrylate. More specifically, for example, di(2-(meth)acryloyloxyethyl) isocyanurate, tri(2-(meth)acryloyloxyethyl) isocyanurate, alkylene oxide-modified products thereof, caprolactone-modified products and the like can be mentioned. These isocyanuric acid (meth)acrylates can be used alone or in combination of two or more kinds.

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

<(C) Photopolymerization initiator>
The photosensitive resin composition of this embodiment contains (C) a photopolymerization initiator. If (C) does not contain a photopolymerization initiator, excellent resolution of vias and adhesive strength with plated copper cannot be obtained. The component (C) is not particularly limited as long as it can polymerize the component (A), and can be appropriately selected from photopolymerization initiators that are commonly used.

Examples of the photopolymerization initiator as the component (C) include benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy. 2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4 Acetophenone-based photopolymerization initiators such as -(methylthio)phenyl]-2-morpholino-1-propanone and N,N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Anthraquinone-based photopolymerization initiators such as chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; thioxanthone type such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone Photopolymerization initiator; ketal-based photopolymerization initiator such as acetophenone dimethyl ketal, 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'-methyldiphenylsulfide; acridine-based photopolymerization initiators such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; 2,4,6- Acylphosphine oxide-based 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. The oxime ester-based photopolymerization initiator of Among these, acetophenone photopolymerization initiators and thioxanthone photopolymerization initiators are preferable, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone are preferable. More preferable.
The component (C) may be used alone or in combination of two or more kinds, and when using plural kinds, it is preferable to use an acetophenone photopolymerization initiator and a thioxanthone photopolymerization initiator in combination, and 2-methyl More preferably, -1-[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2,4-diethylthioxanthone are used in combination.

(Content of component (C))
The content of the 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 the resin components of the photosensitive resin composition. , And more preferably 0.4 to 1.5% by mass. When the content of the component (C) is 0.1% by mass or more, in the interlayer insulating layer formed by using the photosensitive resin composition, the exposed portion is less likely to be eluted during development. %, 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 auxiliary together with the above-mentioned component (C). Examples of the (C′) photopolymerization initiation aid include 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 auxiliary agent. The component (C′) may be used alone or in combination of two or more kinds.
When the photosensitive resin composition of the present embodiment contains the component (C′), the content is preferably 0.01 to 1% by mass, more preferably the total amount of the resin components of the photosensitive resin composition. The content is 0.03 to 0.5% by mass, more preferably 0.05 to 0.3% by mass. The photosensitive resin composition according to the present embodiment may not contain the component (C').

<(D) Thermosetting resin>
The photosensitive resin composition of the present embodiment can further include (D) a thermosetting resin in addition to the above-mentioned components (A) to (C). By including the thermosetting resin (D), in addition to improving the resolution of the via and the adhesive strength with the plated copper, the heat resistance is improved.
Examples of the thermosetting resin include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, dicyclopentadiene resin, silicone. Resin, triazine resin, melamine resin, etc. are mentioned. Moreover, it is not particularly limited to these, and a known thermosetting resin can be used. These thermosetting resins can be used alone or in combination of two or more kinds.
Of these, epoxy resin is preferable. The epoxy resin does not include the one corresponding to the component (A), and in that respect, the epoxy resin used as the thermosetting resin (D) can be said to have no ethylenically unsaturated group. A substance having an epoxy group after satisfying the conditions is included in the component (D).

The epoxy resin as the 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 resin is preferable.

Epoxy resins are also classified into various epoxy resins depending on the difference in the main skeleton, and the epoxy resins of each of the above types are further classified. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin or other bisphenol type epoxy resin; bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin or other bisphenol type novolac type epoxy resin A novolak type epoxy resin other than the bisphenol type novolak type epoxy resin such as a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a biphenyl novolac type epoxy resin; a phenol aralkyl type epoxy resin; a biphenyl aralkyl type epoxy resin; a stilbene type epoxy resin Resin; dicyclopentadiene type epoxy resin; naphthalene type epoxy resin, naphthol novolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthylene ether type epoxy resin and other naphthalene skeleton type epoxy resin; biphenyl type epoxy resin Biphenyl aralkyl type epoxy resin; Xylylene type epoxy resin; Dihydroanthracene type epoxy resin; Dicyclopentadiene type epoxy resin; Alicyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring containing epoxy resin; Cyclohexanedimethanol type epoxy resin; It is classified into trimethylol type epoxy resin; aliphatic chain epoxy resin; rubber modified epoxy resin;

Among them, bisphenol-based epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin is 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 further preferable, and biphenyl type epoxy resin is further preferable.

Commercially available products can be used as these epoxy resins. For example, bisphenol A type epoxy resin (“Epicoat 828EL” and “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H manufactured by Mitsubishi Chemical Corporation”. , "YL983U"), naphthalene type epoxy resin ("IC403" manufactured by DIC Corporation, "HP4032D", "HP4710"), polyfunctional epoxy resin containing naphthalene skeleton ("NC7000" manufactured by Nippon Kayaku Co., Ltd.), naphthol type epoxy resin (new) Nippon Steel & Sumitomo Metal Corporation "ESN-475V"), epoxy resin having a biphenyl structure (Nippon Kayaku Co., Ltd. "NC3000H", "NC3500"), Mitsubishi Chemical Corporation "YX4000", "YX4000HK", "YL6121". )), anthracene type epoxy resin (“YX8800” manufactured by Mitsubishi Chemical Corporation), glycerol type epoxy resin (“ZX1542” manufactured by Nippon Steel & Sumitomo Metal Corporation), naphthylene ether type epoxy resin (“EXA7311-G4 manufactured by DIC Corporation”). ]) and the like.

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

The epoxy-modified polybutadiene preferably has a hydroxyl group at its molecular terminals, more preferably has hydroxyl groups at both molecular terminals, and even more preferably has hydroxyl groups only at both molecular terminals. The number of hydroxyl groups contained in the epoxy-modified polybutadiene is not particularly limited as long as it is 1 or more, but is preferably 1 to 5, more preferably 1 or 2, and further 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.

(In the 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 and n ₂₂ is 0.02. to _{0.30, n 23} is 0.30 to 0.80, _{further, n 21 + n 22 + n} 23 = 1.00 _{and, (n 21 + n 23)} > satisfy _{n 22 .y 21} are brackets Represents the number of structural units within and is an integer of 10 to 250.)

The bonding order of each structural unit in the general formula (2) is in no particular order. That is, the structural unit shown on the left, the structural unit shown at the center, and the structural unit shown on the right may be interchanged, and (a), (b), and (c), respectively. When represented by, -[(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)-( There may be various bond orders such as b)-(c)-]-, -[(c)-(b)-(c)]-[(b)-(a)-(a)-]-.
From the viewpoint of improving the heat resistance, the coefficient of thermal expansion, and the flexibility in addition to the adhesive strength with the plated copper, n ₂₁ is preferably 0.10 to 0.30, and n ₂₂ is preferably 0.10 to 0.30. , N ₂₃ is preferably 0.40 to 0.80. In addition, from the same viewpoint as this, y ₂₁ is preferably an integer of 5 to 500.

In the general formula (2), as a commercially available product of epoxidized polybutadiene, n ₂₁ =0.20, n ₂₂ =0.20, n ₂₃ =0.60, and an integer of y ₂₁ =10 to 250 are available. EPORIDE (registered trademark) PB3600" (manufactured by Daicel Corporation) and the like.

(Content of component (D))
Although the content of the component (D) is not particularly limited, it is preferably 5 to 70% by mass, more preferably 5 to 40% by mass based on the total amount of the resin components of the photosensitive resin composition. , More preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass. When the content of the component (D) is 5% by mass or more, sufficient crosslinking of the photosensitive resin composition is obtained, and the adhesive strength with the plated copper is improved, while when it is 70% by mass or less, the via 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 components (A) to (C). (E) The inclusion of the elastomer improves the resolution of the via and the adhesion strength with the plated copper. Further, the component (E) has an effect of suppressing the flexibility and the decrease in the adhesive strength with the plated copper due to the strain (internal stress) inside the cured product due to the curing shrinkage of the component (A). ..

Examples of the elastomer include, for example, styrene-based elastomer, olefin-based elastomer, polyester-based elastomer, urethane-based elastomer, polyamide-based elastomer, acrylic-based elastomer, silicone-based elastomer, etc., and it is preferable to use at least one selected from these. .. These elastomers are composed of a hard segment component and a soft segment component, and the former tends to contribute to heat resistance and strength, and the latter tends to contribute to flexibility and toughness.
As the component (E), among the above-exemplified elastomers, an olefin-based elastomer, a polyester-based elastomer, and a polyester-based elastomer, from the viewpoint of improving the adhesive strength with plated copper and further improving the compatibility and solubility with the resin component. It is preferable to contain at least one selected from urethane-based elastomers, and it is more preferable to contain urethane-based elastomers. The component (E) is more preferably at least one selected from olefin elastomers, polyester elastomers, and urethane elastomers, and particularly preferably urethane elastomers.

(Styrene elastomer)
Examples of styrene elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers and styrene-ethylene-propylene-styrene block copolymers.

A commercially available product may be used as the styrene-based elastomer, and examples of the commercially available product include, for example, Toughprene, Sorprene T, Asaprene T, Tuftec (these are Asahi Kasei Corporation's “Tuffprene”, “Asuprene” and “Tuftec”). Registered trademark), elastomer AR (manufactured by Aron Kasei Co., Ltd.), Kraton G, perreflex (manufactured by Shell Japan Co., Ltd.), JSR-TR, TSR-SIS, Dynaron (manufactured by JSR Co., Ltd.), Denka STR (Denka Co., Ltd.), Quintac (Nippon Zeon Co., Ltd., "Quintac" is a registered trademark), TPE-SB series (Sumitomo Chemical Co., Ltd.), Lavalon (Mitsubishi Chemical Co., Ltd., "Lavalon" is registered) Trademark), Septon, High Blur (above, manufactured by Kuraray Co., Ltd., "Septon" and "High Blur" are registered trademarks), Sumiflex (Sumitomo Bakelite Co., Ltd.), Rheostomer, Actimer (Richken Technos Co., Ltd., "Rheostomer" "And "Actimer" are registered trademarks) and the like.

(Olefin elastomer)
Examples of the olefin 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 its molecular end, and preferably has a hydroxyl group at its molecular end.
Examples of the olefin elastomer include polyethylene, polybutadiene, hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisopropylene, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like. In addition, 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, methylene norbornene, ethylidene norbornene, butadiene and isoprene. Copolymers and the like are also included. Furthermore, a carboxy-modified NBR obtained by copolymerizing methacrylic acid with a butadiene-acnylonitrile copolymer can also be used.
The olefin elastomer preferably has a number average molecular weight of 1,000 to 5,000, more preferably 1,500 to 3,500.

A commercially available product may be used as the olefin elastomer, and examples of the commercially available product include Mirastoma (manufactured by Mitsui Chemicals, Inc., trade name), EXACT (manufactured by ExxonMobil, trade name), ENGAGE (The Dow Chemical Company, trade name), Poly ip, Poly bd (Idemitsu Kosan Co., Ltd., trade name), Hydrogenated styrene-butadiene rubber "DYNABON HSBR" (JSR Co., Ltd. trade 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), epoxidation partially epoxidized polybutadiene Examples include polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd., trade name), PB-4700, PB-3600 (manufactured by Daicel Co., Ltd., trade name).

(Polyester elastomer)
Examples of polyester-based elastomers include those obtained by polycondensing a dicarboxylic acid or its derivative and a diol compound or its derivative.
Specific examples of the dicarboxylic acid include, for example, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; hydrogen atoms in the aromatic ring of the aromatic dicarboxylic acid are substituted with a methyl group, an ethyl group, a phenyl group, or the like. And aromatic dicarboxylic acids; adipic acid, sebacic acid, dodecanedicarboxylic acid, and other aliphatic dicarboxylic acids having 2 to 20 carbon atoms; cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids; As the dicarboxylic acid, it is also preferable to use a natural product-derived dimer acid from the viewpoint of improving the resolution of vias, the adhesion strength with plated copper, and the insulation reliability. The dicarboxylic acids may be used alone or in combination of two or more.
Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol; 1,4 A cycloaliphatic diol such as cyclohexanediol; and the like. The diol compounds may be used alone or in combination of two or more.
The polyester elastomer preferably has a number average molecular weight of 900 to 30,000, more preferably 1,000 to 25,000, and even more preferably 5,000 to 15,000.

A commercially available product may be used as the polyester-based elastomer, and as the commercially available product, for example, Hytrel (manufactured by Toray DuPont Co., Ltd., "Hytrel" is a registered trademark), Perprene (manufactured by Toyobo Co., Ltd., "Perprene" is Registered trademark), Espel (manufactured by Hitachi Chemical Co., Ltd., "Esper" 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 a diisocyanate, and a soft segment composed of a polymer (long chain) diol and a diisocyanate.
Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly(1,4-butylene adipate), poly(ethylene-1,4-butylene adipate), polycaprolactone, poly(1,6-hexadiene). Xylene carbonate), poly(1,6-hexylene neopentylene adipate) and the like. The number average molecular weight of the polymeric (long-chain) diol is preferably 500 to 10,000.
Examples of the short chain diol include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A and the like. The number average molecular weight of the short chain diol is preferably 48 to 500.

A commercially available product may be used as the urethane-based elastomer, and examples of the commercially available product include PANDEX T-2185, T-2983N (above, manufactured by DIC Co., Ltd.), Miractolan series (manufactured by Nippon Miractoran 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)
As the polyamide elastomer, for example, polyamide is a hard segment component, polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate. Block copolymers containing, as a soft segment component, polymethacrylate, polyurethane, silicone rubber or the like.

A commercially available product may be used as the polyamide-based elastomer, and examples of the commercially available product include UBE polyamide elastomer (manufactured by Ube Industries, Ltd.), Daiamide (manufactured by Daicel-Evonik Ltd., “Daiamide” is a registered trademark), PEBAX. (Manufactured by Toray Industries, Inc.), Guriron ELY (manufactured by Ems Chemie Japan, "Griron" is a registered trademark), Novamid (manufactured by Mitsubishi Chemical Co., Ltd.), Grelax (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. Preferable examples of the acrylate ester include ethyl acrylate, butyl acrylate, methoxyethyl acrylate and ethoxyethyl acrylate. As the crosslinking point monomer, glycidyl methacrylate, allyl glycidyl ether, etc. may be copolymerized, and further, acrylonitrile, ethylene, etc. may be copolymerized. Specific examples thereof include an acrylonitrile-butyl acrylate copolymer, an acrylonitrile-butyl acrylate-ethyl acrylate copolymer, and an acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer.

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

A commercially available product may be used as the silicone-based elastomer, and examples of the commercially available product include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series and SH series (all manufactured by Toray Dow Corning Co., Ltd.). ) Is mentioned.

(Other elastomers)
Further, 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 preferable.

(Content of component (E))
The content of the 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 the resin components of 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 the component (E) is 2% by mass or more, the adhesive strength with the plated copper is improved, and when it is 30% by mass or less, the resolution of the via and the adhesive strength with the plated copper are improved. become.

<(F) Inorganic filler>
The photosensitive resin composition of this embodiment may contain (F) an inorganic filler. The inclusion of the inorganic filler (F) improves the resolution of the vias and improves the low thermal expansion, so that the occurrence of warpage can be further reduced. In the thermosetting resin composition that has been conventionally used as an interlayer insulating layer of a multilayer printed wiring board, low thermal expansion has been achieved by containing an inorganic filler, but the photosensitive resin composition contains an inorganic filler. If included, the inorganic filler causes light scattering and interferes with development. Therefore, it has been difficult to reduce the thermal expansion by adding a large amount. As described above, with respect to the inclusion of the inorganic filler, there is a new problem unique to the photosensitive resin composition, but the photosensitive resin composition of the present embodiment is considered to contain a large amount of the inorganic filler. Also, the resolution of vias is high. As a result, in the present embodiment, by using the inorganic filler (F), it is possible to achieve high resolution of vias as well as low thermal expansion.

Examples of the component (F) include 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 ₃ ). 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.TiO ₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O ₃ ), spinel (MgO.Al ₂ O ₃ ), mullite (3Al) ₂ O ₃ · ₂ SiO ₂ ), cordierite (2MgO·2Al ₂ O ₃ /5SiO ₂ ), talc (3MgO·4SiO ₂ ·H ₂ O), aluminum titanate (TiO ₂ ·Al ₂ O ₃ ), yttria-containing zirconia _{(Y 2 O 3 · ZrO 2} ), barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), barium sulfate (BaSO _4), calcium sulfate (CaSO _4), zinc oxide (ZnO), magnesium titanate (MgO.TiO ₂ ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like. The component (F) may be used alone or in combination of two or more kinds.

The average particle diameter of the inorganic filler (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, and still more preferably 0.1 to 2 μm from the viewpoint of resolution of vias. In the present specification, the average particle size of the (B) inorganic filler 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 the following measurement. To do.
First, after diluting (or dissolving) the photosensitive resin composition by 1,000 times with methyl ethyl ketone, using a submicron particle analyzer (Beckman Coulter, Inc., trade name: N5), ISO 13321 In accordance with the above, particles dispersed in a solvent having a refractive index of 1.38 were measured, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution was taken as the volume average particle diameter, and this was the average of the inorganic fillers. The particle size. Further, the component (F) contained in the photosensitive resin film and the interlayer insulating layer provided on the carrier film was also diluted (or dissolved) 1,000 times (volume ratio) with the solvent as described above. Then, it can be measured by using the submicron particle analyzer.

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

<(G) Thermal polymerization initiator>
The photosensitive resin composition of the present embodiment may further contain (G) a thermal polymerization initiator in addition to the above-mentioned components (A) to (C). (G) The inclusion of the thermal polymerization initiator improves the resolution of the via and the adhesive strength with the plated copper.
The thermal polymerization initiator is not particularly limited, but for example, diisopropylbenzene hydroperoxide “Perk Mill P” (trade name, manufactured by NOF CORPORATION (hereinafter the same)), cumene hydroperoxide “Perk Mill H”. , Hydroperoxide-based thermal polymerization initiators such as t-butyl hydroperoxide “Perbutyl H”; α,α-bis(t-butylperoxy-m-isopropyl)benzene “Perbutyl P”, dicumyl peroxide “Perkmill D”. , 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane "Perhexa 25B", t-butylcumyl peroxide "Perbutyl C", di-t-butyl peroxide "Perbutyl D", 2 ,5-Dimethyl-2,5-bis(t-butylperoxy)hexyne-3 "Perhexin 25B", t-butylperoxy-2-ethylhexanoate "Perbutyl O", etc. Initiator: Ketone peroxide thermal polymerization initiator: Peroxyketal thermal polymerization initiator such as n-butyl 4,4-di-(t-butylperoxy)valerate "Perhexa V"; Diacyl peroxide thermal polymerization Initiator: Peroxydicarbonate-based thermal polymerization initiator; Organic peroxide such as peroxyester-based thermal polymerization initiator; 2,2'-azobisisobutyl nitrile, 2,2'-azobis(2-cyclopropyl pro Azo compounds such as pionitrile) and 2,2′-azobis(2,4-dimethylvaleronitrile); and the like. Among them, dialkylperoxaside-based thermal polymerization initiators are preferable from the viewpoint that the photopolymerizability is not hindered and the effect of improving the physical properties and characteristics of the photosensitive resin composition is large, and 2,5-dimethyl-2, More preferred is 5-bis(t-bitylperoxy)hexyne-3.
The thermal polymerization initiators may be used alone or in combination of two or more.

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

<(H) pigment>
The photosensitive resin composition of the present embodiment may contain a pigment as a component (H) according to a desired color in order to adjust the photosensitivity and improve the appearance such as hiding the conductor pattern. As the component (H), a colorant that develops a desired color may be appropriately selected and used, and examples thereof include phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black. Well-known coloring agents such as

(Content of (H) component)
When the photosensitive resin composition of the present embodiment contains the component (H), the content is the solid content of the photosensitive resin composition from the viewpoint of facilitating identification of the manufacturing apparatus and further hiding the conductor pattern. The total amount is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and further 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 obtained insulating layer. Good.
Specific examples of the component (I) include, for example, 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; diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, 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-based epoxy resin curing agents such as 2,4-diamino-6-xylyl-S-triazine; trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N- Methyl)melamine, 2,4,6-tris(dimethylaminophenol), tetramethylguanidine, m-aminophenol and other tertiary amine type epoxy resin curing agents; polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol novolac 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 above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, Examples thereof include triphenylsulfonium hexafluoroantimonate and 2,4,6-triphenylthiopyrylium hexafluorophosphate.

(Content of component (I))
When the photosensitive resin composition of the present embodiment contains the component (I), the content thereof is preferably 0.01 to 20% by mass, more preferably 0, based on the total amount of the resin components of the photosensitive resin composition. 0.1 to 10% by mass, more preferably 0.5 to 2% by mass.

<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment, if necessary. As the diluent, for example, an organic solvent or the like can be used. Examples of the organic solvent 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 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 organic solvents; aliphatic hydrocarbon organic solvents such as octane and decane; petroleum organic solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. The diluent may be used alone or in combination of two or more kinds.

(Content of diluent)
The content of the diluent is appropriately adjusted such 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 further preferably 65 to 75% by mass. Just select it. By adjusting the amount of the diluent used in this way, the coating property of the photosensitive resin composition is improved, and it becomes possible to easily form a finer pattern.

<Other additives>
In the photosensitive resin composition of the present embodiment, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; a thickening agent such as benton or montmorillonite; a silicone antifoaming agent, Various known conventional additives such as a defoaming agent such as a fluorine-based defoaming agent and a vinyl resin-based defoaming agent; a silane coupling agent can be incorporated. Further, a flame retardant such as a brominated epoxy compound, an acid-modified brominated epoxy compound, an antimony compound and a phosphate compound of a phosphorus compound, an aromatic condensed phosphoric acid ester, a halogen-containing condensed phosphoric acid ester and the like can be contained.

The photosensitive resin composition of the present embodiment can be obtained by kneading and mixing each component with a roll mill, a bead mill or the like.
Here, the photosensitive resin composition of the present embodiment may be used in a liquid form or a film form.
When used as a liquid, the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include a printing method, a spin coating method, a spray coating method, a jet dispensing method, an inkjet method, and a dip coating method. Various coating methods can be mentioned. Among these, a printing method and a spin coating method may be appropriately selected from the viewpoint of forming the photosensitive layer more easily.
When used as a film, it can be used, for example, in the form of a photosensitive resin film described later, and in this case, a photosensitive layer having a desired thickness is formed by laminating on a carrier film using a laminator or the like. be able to. 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 composed of the photosensitive resin composition of the present embodiment, and is preferably used for forming a photosensitive layer which will be an interlayer insulating layer, for example. The photosensitive resin film of the embodiment may be a mode in which the photosensitive resin film is provided on the 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, preferably 1 to 100 μm, more preferably 1 to 50 μm. , And more preferably 5 to 40 μm.

The photosensitive resin film of the present embodiment, for example, a carrier film, the photosensitive resin composition of the present embodiment, a known coating such as comma coater, bar coater, kiss coater, roll coater, gravure coater, die coater It can be obtained by forming a photosensitive layer which later becomes an interlayer insulating layer by coating and drying with an apparatus.
Examples of the carrier film 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 the photosensitive resin film of the present embodiment, a protective film may be provided on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective film, for example, a polymer film of polyethylene, polypropylene or the like can be used. Further, a polymer film similar to the above-mentioned carrier film may be used, or a different polymer film may be used.

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

The photosensitive resin film of this embodiment is suitable for the interlayer insulating layer of a multilayer printed wiring board because it has excellent resolution of vias, adhesive strength with plated copper, and insulation reliability. That is, the photosensitive resin film of the present embodiment is suitable as a photosensitive resin film for an interlayer insulating layer, which is preferably used for forming an interlayer insulating layer. In addition, the photosensitive resin film for interlayer insulation layers may be generally called an interlayer insulation film.

[Multilayer Printed Wiring Board and Manufacturing Method Thereof]
The multilayer printed wiring board of the present embodiment includes an interlayer insulating layer formed by using the photosensitive resin composition (photosensitive resin film for interlayer insulating layer) of the present embodiment described above. 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, for example, the following book It can be easily manufactured by the method for manufacturing a multilayer printed wiring board of the embodiment.

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

(Laminating process (1))
In the laminating step (1), for example, using a vacuum laminator, the photosensitive resin film (photosensitive resin film for interlayer insulating layer) of the present embodiment is laminated on one side or both sides of the circuit board (the board 101 having the circuit pattern 102). It is a process to do. As the vacuum laminator, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a vacuum pressure type laminator manufactured by Meiki Co., Ltd., a roll type dry coater manufactured by Hitachi Ltd., a vacuum laminator manufactured by Hitachi Chemical Electronics Co., Ltd., etc. Can be mentioned.

When the protective film is provided on the photosensitive resin film, after peeling or removing the protective film, the photosensitive resin film is pressure-bonded and heat-bonded to the circuit board so that the photosensitive resin film contacts the circuit board and laminated. can do.
For the laminate, for example, after the photosensitive resin film and the circuit board are preheated as necessary, the pressure bonding temperature is 70 to 130° C., the pressure bonding pressure is 0.1 to 1.0 MPa, and the air pressure is 20 mmHg (26.7 hPa) or less. It can be carried out under reduced pressure, but is not particularly limited to this condition. The laminating method may be a batch method or a continuous method using rolls.
Finally, the photosensitive resin film (hereinafter sometimes referred to as a photosensitive layer) laminated on the circuit board is cooled to around room temperature to form the interlayer insulating layer 103. The carrier film may be peeled off here, or may be peeled off after exposure as described later.

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

A known light source can be used as the light source of the actinic ray. Specific examples of the light source include carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, solid-state lasers such as YAG lasers, and ultraviolet rays or visible rays such as semiconductor lasers. Things; and the like. The exposure amount is appropriately selected depending on the light source used, the thickness of the photosensitive layer, etc., but in the case of ultraviolet irradiation from a high pressure mercury lamp, for example, when the thickness of the photosensitive layer is 1 to 100 μm, it is usually about 10 to 1,000 J/m ^2. Is preferable and 15-500 J/m< ² > is more preferable.

In the development, the uncured portion of the photosensitive layer is removed from the substrate, so that the interlayer insulating layer made of a photocured cured product is formed on the substrate.
When the carrier film is present on the photosensitive layer, the carrier film is removed, and then the unexposed portion is removed (developed). The developing method includes wet development and dry development, and either of them may be adopted, but wet development is widely used, and wet development can also be adopted in the present embodiment.

In the case of wet development, development is performed by a known development method using a developing solution corresponding to the photosensitive resin composition. Examples of the developing method include methods using a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking dipping and the like. Among them, the spray method is preferable from the viewpoint of improving the resolution, and the high pressure spray method is more preferable among the spray methods. The development may be performed by one method, but may be performed by combining two or more methods.
The constitution of the developer may be appropriately selected according to the constitution of the photosensitive resin composition. For example, an alkaline aqueous solution, a water-based developer and an organic solvent-based developer can be mentioned, and among these, the alkaline aqueous solution is preferable.

In the photo via formation step (2), after exposure and development, post UV cure 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. By performing post thermal curing at a temperature of (preferably 120 to 200° C.) as necessary, the interlayer insulating layer may be further cured, and it is preferable to do so.
As described above, the interlayer insulating layer having the via 104 is formed. There is no particular limitation on the shape of the via. Explaining with a cross-sectional shape, for example, a quadrangle, an inverted trapezoid (the upper side is longer than the lower side), etc. can be mentioned. , Square and the like. In the formation of vias by the photolithography method in the present embodiment, it is possible to form vias having an inverted trapezoidal cross section (the upper side is longer than the lower side), and in this case, the throwing power of the plated copper to the via wall surface becomes high. Is preferred.

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

(Roughening process (3))
In the roughening treatment step (3), the surfaces of the via and the interlayer insulating layer are roughened with a roughening solution. When smear occurs in the photovia forming step (2), the smear may be removed by the roughening liquid. The roughening process and the 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, sodium permanganate roughening liquid, etc.), and sodium fluoride/chromium/sulfuric acid roughening liquid.
By the roughening treatment, uneven anchors are formed on the surfaces of the via and the interlayer insulating layer.

(Circuit pattern forming step (4))
The circuit pattern forming step (4) is a step of forming a circuit pattern on the interlayer insulating layer after the roughening treatment step (3).
The circuit pattern is preferably formed by a semi-additive process from the viewpoint of forming fine wiring. Via the semi-additive process, the circuit pattern is formed and the via is conducted.

In the semi-additive process, first, a seed layer 105 is formed by applying an electroless copper plating process on the via bottom, the via wall surface, and the entire surface of the interlayer insulating layer after the roughening step (3) using a palladium catalyst or the like. To form. The seed layer is for forming a power feeding layer for performing electrolytic copper plating, and is preferably formed with a thickness of about 0.1 to 2.0 μm. If the thickness of the seed layer is 0.1 μm or more, it tends to be possible to suppress a decrease in 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 etching amount at that time, and there is a tendency that damage given to the wiring at the time of etching can be suppressed.

The electroless copper plating treatment is performed by depositing metallic copper on the surfaces of the via and the interlayer insulating layer by the reaction of copper ions and the reducing agent.
The electroless plating treatment method and the electrolytic plating treatment method may be known methods, and are not particularly limited, but the catalyst in the electroless plating treatment step is preferably a palladium-tin mixed catalyst, The primary particle size is preferably 10 nm or less. Further, the plating composition in the electroless plating treatment step preferably contains hypophosphorous acid as a reducing agent.
A commercially available product can be used as the electroless copper plating solution, and examples of the commercially available product include "MSK-DK" manufactured by Atotech Japan Co., Ltd. and "Sulcap (registered trademark) PEA ver. 4" manufactured by Uemura Kogyo Co., Ltd. And the like.

After performing the above electroless copper plating treatment, a dry film resist is thermocompression-bonded onto the electroless copper plating with a roll laminator. The thickness of the dry film resist must be higher than the wiring height after electrolytic copper plating, and from this viewpoint, a dry film resist having a thickness of 5 to 30 μm is preferable. As the dry film resist, "Photec" series manufactured by Hitachi Chemical Co., Ltd. is used.
After the thermocompression bonding of the dry film resist, 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 device and light source as those that can be used when forming the vias in the photosensitive resin film. After the exposure, the carrier film on the dry film resist is peeled off and developed using an alkaline aqueous solution to remove the unexposed portion and form a resist pattern 106. After this, an operation of removing the development residue of the dry film resist may be performed using plasma or the like, if necessary.
After the development, electrolytic copper plating is performed to form the copper circuit layer 107 and to perform via filling.

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

After the dry film resist is peeled off or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment sufficiently thermosets the unreacted thermosetting component, thereby further improving the adhesive strength with the plated copper, the insulation reliability, and the curing characteristics. Although the thermosetting conditions vary depending on the type of the resin composition and the like, 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 steps for manufacturing a printed wiring board by the photo via method, but this process is repeated to manufacture a substrate depending on the number of interlayer insulating layers required. Then, a solder resist layer 108 is preferably formed on the outermost layer.

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

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

1. Evaluation of resolution of via (1) Preparation of laminated body for evaluation Printed wiring board substrate (trade name "MCL-E-679" manufactured by Hitachi Chemical Co., Ltd.) in which a copper foil having a thickness of 12 µm is laminated on a glass epoxy substrate. ) Is treated with a roughening pretreatment liquid (manufactured by Mec Co., Ltd., trade name "CZ-8100"), washed with water and dried to obtain a roughened pretreatment printed wiring board substrate. It was Next, the protective film is peeled off from the carrier film and the photosensitive resin film with the protective film produced in each Example and Comparative Example, and the exposed photosensitive resin film is a substrate for printed wiring board that has been subjected to the roughening pretreatment. After being placed so as to come into contact with the copper foil of No. 3, it was laminated using a press-type vacuum laminator (manufactured by Meiki Co., Ltd., trade name "MVLP-500"). The laminating conditions were a hot press plate temperature of 70° C., a vacuuming time of 20 seconds, a laminating press time of 30 seconds, an atmospheric pressure of 4 kPa or less, and a pressure bonding pressure of 0.4 MPa. After the laminating treatment, the laminate was left at room temperature for 1 hour or longer to obtain a laminate for evaluation in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil surface of the printed wiring board substrate.
(2) Sensitivity measurement of photosensitive resin film After peeling and removing the carrier film of the evaluation laminate obtained above, a 41-step step tablet is arranged, and a direct imaging exposure device "DXP" using a super high pressure mercury lamp as a light source is provided. -3512" (Oak Seisakusho Co., Ltd.) was used for exposure. The exposure pattern used was a pattern in which dots having a diameter of 30 to 100 μm were arranged in a grid pattern.
After the exposure, the mixture was allowed to stand at room temperature for 30 minutes, and then the unexposed area of the photosensitive resin composition was spray-developed for 60 seconds using a 1% by mass aqueous sodium carbonate solution at 30°C. After development, the exposure energy amount at which the 41-step step tablet had a gloss remaining step number of 10.0 was defined as the sensitivity (unit: mJ/cm ² ) of the photosensitive resin film. 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 The resolution was evaluated by observing the via pattern using an optical microscope after exposure with an exposure energy amount such that the number of steps is 10.0 and then spray development. The following criteria were used to evaluate the openings of the 50 μm and 60 μm via portions of the dot pattern. The minimum diameter of the opening is 60 μm or less, that is, the judgment of “A” and “B” shows that the via has excellent resolution, and the minimum diameter of the opening exceeds 60 μm or a cured film is obtained. If there is not, that is, the judgment 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 more than 60 μm.
D: A cured film could not be obtained.

2. Evaluation of Adhesive Strength (Peel Strength) with Plated Copper (1) Preparation of Laminate for Evaluation and Sensitivity Measurement of Photosensitive Resin Film [1. [1] and (2) in [Evaluation of Resolution], the exposure machine used was a parallel light exposure machine using an ultra-high pressure mercury lamp as a light source (Oak Seisakusho Co., Ltd., trade name “EXM-1201”). ) Except that the above [1. [Evaluation of Resolution], the same operation as the steps (1) and (2) is performed to obtain an exposure energy amount at which the number of steps of remaining gloss step becomes 10.0, and this is determined as the sensitivity (unit; mJ/cm ² ).
(2) Exposure Step and Development Step Next, the carrier film of the evaluation laminate was peeled off and the exposed surface of the photosensitive resin film was exposed to light over the entire surface with the exposure energy amount obtained above to obtain a photosensitive resin. An insulating layer formed by curing the film was formed. After the exposure, the mixture was allowed to stand at room temperature for 30 minutes, and then the unexposed portion of the photosensitive resin film was spray-developed for 60 seconds with a 1% by mass aqueous solution of sodium carbonate at 30°C.
(3) Post-cure treatment Subsequently, a high-pressure mercury lamp lamp irradiation type UV conveyor device (manufactured by Oak Manufacturing Co., Ltd.) is used to perform post-UV cure at a conveyor speed at which 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 Scientific Co., Ltd.).
(4) Roughening treatment The evaluation laminate after the post-cure treatment was treated with a swelling liquid "Swelling dip securigant P" at 70°C for 5 minutes, and then a roughening liquid "dosing securigant P500J". Was used for 10 minutes at 70° C., and further, a neutralizing solution “Reduction Conditioner Seculigant P500” was used for 5 minutes at 40° C. for roughening. The swelling liquid, the roughening liquid, and the neutralizing liquid were all manufactured by Atotech Japan Co., Ltd.
(5) Plating Treatment Electroless plating treatment is applied to the evaluation laminate after the roughening treatment at 30° C. for 20 minutes using an electroless plating solution “Pregant MSK-DK” (manufactured by Atotech Japan Co., Ltd.). Then, using an electroplating solution “Caparaside HL” (manufactured by Atotech Japan Co., Ltd.), electroplating treatment is performed at 24° C. and 2 A/dm ² for 1 hour to form a plated copper layer on the insulating layer. Thus, an evaluation board for measuring the adhesive strength with the plated copper was produced. The thickness of plated copper formed by the plating treatment was 25 μm.
(6) Measurement of Adhesive Strength (Peel Strength) with Plated Copper Adhesive strength with plated copper was measured by measuring vertical peel strength at 23° C. according to JIS C6481 (1996). The adhesive strength with plated copper was evaluated according to the following criteria. If the adhesive strength with the plated copper is 0.40 kN/m or more, it shows that it has excellent performance, that is, if it is judged as "A", it has the excellent adhesive strength with the plated copper. , 0.40 kN/m, that is, the judgments of “B” and “C” fail.
A: The adhesive strength with the plated copper was 0.40 kN/m or more.
B: The adhesive strength with the plated copper was less than 0.40 kN/m and 0.30 kN/m or more.
C: The adhesive strength with the plated copper was less than 0.30 kN/m.

<Synthesis Example 1> (A1-1) Synthesis of acid-modified vinyl group-containing epoxy derivative 1 Bisphenol F novolac type epoxy resin (in the general formula (I), a structural unit in which Y ¹ is a glycidyl group and R ¹ is a hydrogen atom) Bisphenol F novolac type epoxy resin containing 350 parts by mass of (a1) component, 70 parts by mass of acrylic acid (corresponding to (a2) component), 0.5 parts by mass of methylhydroquinone, 120 parts by mass of carbitol acetate. After charging, the mixture was heated to 90° C. and stirred to cause a reaction, and the mixture was completely dissolved.
Next, the obtained solution was cooled to 60° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100° C. and reacted until the acid value of the solution became 1 mgKOH/g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the component (a3)) and 85 parts by mass of carbitol acetate were added, heated to 80° C. and reacted for 6 hours.
Then, it cooled to room temperature and obtained the acid-modified bisphenol F novolac type epoxy acrylate (corresponding to the component (A1-1)) having a solid content concentration of 73 mass% as the acid-modified vinyl group-containing epoxy derivative 1.

<Measurement method of weight average molecular weight>
The weight average molecular weight was measured with the following GPC measuring device and measuring conditions, and the value converted using a calibration curve of standard polystyrene was taken as the weight average molecular weight. The calibration curve was prepared using 5 sample sets (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) as standard polystyrene.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is a differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Corporation Made by company (measurement conditions)
Solvent: Tetrahydrofuran (THF)
Measurement temperature: 40℃
Flow rate: 0.35 ml/min Sample concentration: 10 mg/THF 5 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 placed in a flask equipped with a thermometer and a stirrer to be dissolved. Then, while performing nitrogen gas purging, the temperature was raised to 65° C., the pressure was reduced to an azeotropic pressure, 122 parts by mass of a 49 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours, and the mixture was stirred for 0.5 hour. During this time, the distillate distilled off azeotropically was separated by a Dean Stark trap to remove the aqueous layer, and the organic layer was returned to the reaction system for reaction. Then, unreacted epichlorohydrin was distilled off under reduced pressure to remove the crude epoxy resin. To the obtained crude epoxy resin, 1000 parts by mass of methyl isobutyl ketone and 100 parts by mass of n-butanol were added and dissolved, and 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added to this 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 system was dehydrated by azeotropic distillation, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain a transparent liquid epoxy resin a-1: 350 parts by mass. 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 and reacted by heating to 90° C. and stirring to completely dissolve the mixture. The resulting solution was cooled to 60° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100° C. and reacted until the acid value of the solution reached 1 mgKOH/g, and tetrahydrophthalic anhydride (THPAC) was added to the solution. ) (C) 98 parts by mass and 850 parts by mass of carbitol acetate were added, and the mixture was heated to 80° C. and reacted for 6 hours. Then, the mixture was cooled to room temperature to obtain a THPAC-modified cresol novolac-type epoxy acrylate epoxy resin having a solid content concentration of 73 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)
The composition was blended according to the blending composition shown in Table 1 and kneaded with a three-roll mill to prepare a photosensitive resin composition. In each example, carbitol acetate was appropriately added to adjust the concentration to obtain a photosensitive resin composition having a solid content 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. It was applied as described above 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 oriented polypropylene film (MA-411, manufactured by Oji Ftex Co., Ltd., trade name) is provided on the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film. The photosensitive resin film was prepared by laminating the carrier film and the protective film together as a protective film.
Each evaluation was performed according to the above method using the produced photosensitive resin film. The evaluation results are shown in Table 1.

The components used in each example are 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: the one obtained in Synthesis Example 1 ((A1-1 ) Corresponds to the component).
-Acid-modified vinyl group-containing epoxy derivative 2: the one obtained in Synthesis Example 2 (corresponding to the component (A1-1)).
-Polyfunctional vinyl monomer: dipentaerythritol pentaacrylate (corresponds to (Aiii) component)
Component (B): Photopolymerizable compound having ethylenically unsaturated group and isocyanuric skeleton, isocyanuric acid acrylate 1: tris(2-acryloyloxyethyl) isocyanuric acid (“FA-731A” (manufactured by Hitachi Chemical Co., Ltd.))
-Isocyanuric acid acrylate 2: tris(2-acryloyloxyethyl) isocyanuric acid ("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.))
Component (C): photopolymerization initiator/photopolymerization initiator 1: acetophenone-based photopolymerization initiator (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, "IRGACURE 907" (Manufactured by BASF)
Photopolymerization initiator 2: thioxanthone type photopolymerization initiator (2,4-diethylthioxanthone, "KAYACURE DETX-S" (manufactured by Nippon Kayaku Co., Ltd.))
Component (D): thermosetting resin/epoxy resin: biphenyl type epoxy resin (“YX-4000” (manufactured by Mitsubishi Chemical Corporation))
Component (E): Elastomer/Elastomer 1: Epoxidized polybutadiene ("PB-4700" (manufactured by Daicel Corporation))
・Elastomer 2: Polyester resin ("Esper 1108" (manufactured by Hitachi Chemical Co., Ltd.))
Component (F): 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 the resolution of vias and the adhesive strength with plated copper. On the other hand, the resin composition of Comparative Example 1 which does not contain the component (B) has a poor adhesive strength with plated copper, and the resin composition of Comparative Example 2 which does not contain a photopolymerization initiator has a resolution of vias and The adhesive strength with the plated copper was 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, and (C) a photopolymerization initiator A photosensitive resin composition containing. (A) a photopolymerizable compound having an ethylenically unsaturated group and not having an isocyanuric skeleton, (A1) a photopolymerizable compound having an acidic substituent together with an ethylenically unsaturated group, and having no isocyanuric skeleton The photosensitive resin composition according to claim 1, which comprises: The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerizable compound (B) having an ethylenically unsaturated group and an isocyanuric skeleton contains isocyanuric acid (meth)acrylate. The photopolymerizable compound having the (B) ethylenically unsaturated group and an isocyanuric skeleton contains at least one selected from isocyanuric acid di(meth)acrylate and isocyanuric acid tri(meth)acrylate. The photosensitive resin composition according to any one of items. The photosensitive resin composition according to claim 1, further comprising (D) a thermosetting resin. The photosensitive resin composition according to claim 1, further comprising (E) an elastomer. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (F) an inorganic filler. The content of the photopolymerizable compound having the (A) 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 the item. Content of the said (B) photopolymerizable compound which has an ethylenically unsaturated group and an isocyanuric skeleton is 0.5 to 15 mass% on the basis of solid content total amount, In any one of Claims 1-8. The photosensitive resin composition described. The photosensitive resin composition according to any one of claims 1 to 9, wherein the content of the (C) photopolymerization initiator is 0.1 to 15 mass% based on the total solid content. The photosensitive resin composition according to claim 1, which is used for forming a photo via. 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 claim 1. 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 claim 1. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to claim 13. A semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board according to claim 15. The manufacturing method of the multilayer printed wiring board which has the following processes (1)-(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 a via by exposing and developing the photosensitive resin film laminated in the 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.