JP2020166031A - Photosensitive resin composition, photosensitive resin film, multilayer printed board and semiconductor package, and method for manufacturing multilayer printed board - Google Patents

Abstract

To provide a photosensitive resin composition being excellent in via resolution, adhesive strength to plated copper and insulation reliability.SOLUTION: A photosensitive resin composition contains (A) a photopolymerizable compound having an ethylenically unsaturated group (excluding one having an epoxy group or oxetanyl group), (B) a compound having an epoxy group or oxetanyl group and an ethylenically unsaturated group, 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 and a semiconductor package, and a method for manufacturing a multilayer printed wiring board.

In recent years, the miniaturization and high performance of electronic devices have progressed, and the density of multilayer printed wiring boards has been increasing due to an increase in the number of circuit layers and miniaturization of wiring. In particular, the density of semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted is remarkable, and in addition to miniaturization of wiring, thinning of insulating film and interlayer connection are used. Further reduction in the diameter of vias (also called via holes) is required.

As a method for manufacturing a printed wiring board that has been conventionally adopted, there is 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. .. For multi-layer printed wiring boards, the semi-additive method, in which the circuit is formed by plating as the circuit becomes finer, has become the mainstream.
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". (2) Next, vias for interlayer connection are formed by laser processing, and desmear treatment and roughening treatment are performed by alkaline permanganate treatment or the like. (3) After that, the substrate is subjected to electrolytic copper plating treatment, a pattern is formed using a resist, and then electrolytic copper plating is performed to form a copper circuit layer. (4) Next, a copper circuit has been formed by stripping the resist and performing flash etching of the electroless layer.

As described above, laser processing is the mainstream method for forming vias in the interlayer insulating layer formed by curing a thermosetting resin film, and the diameter of vias is reduced by laser irradiation using a laser processing machine. Has reached its limit. Furthermore, in the formation of vias by a laser processing machine, it is necessary to form each via hole one by one, 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 vias and the manufacturing is performed. There is a problem of inefficiency.

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

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

Patent Document 2 has a problem of suppressing a decrease in 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. In addition to the above, it is said that the resolution of vias and the adhesion to the substrate and chip parts of silicon material are also issues, and these have been solved. However, there is room for further improvement in terms of via resolution, adhesive strength with plated copper, and insulation reliability.
Similarly, as the material of the interlayer insulating layer, it is conceivable to divert a photosensitive resin composition or the like which is a material of a conventional solder resist, but the interlayer insulating layer has characteristics that are not necessary for the solder resist (for example, Since insulation reliability between layers, adhesive strength with plated copper, high heat resistance that can withstand multiple heatings during multilayer formation, high dimensional accuracy of via shape, etc.) are required, it can withstand practical use as an interlayer insulating layer. Whether or not it is difficult to predict, and it cannot be easily diverted.

Therefore, an object of the present invention is a photosensitive resin composition having excellent via resolution, adhesive strength with plated copper, and insulation reliability, a photosensitive resin composition for forming photovia, and a photosensitive resin composition for an interlayer insulating layer. Is to provide. Further, the present invention provides a photosensitive resin film made of the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer, a multilayer printed wiring board and a semiconductor package, and a method for manufacturing the multilayer printed wiring board. To provide.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following invention, and have completed the present invention.
That is, the present invention relates to the following [1] to [14].
[1] (A) Photopolymerizable compounds having an ethylenically unsaturated group (excluding those having an epoxy group or an oxetanyl group),
(B) A compound having an epoxy group or an oxetanyl group and an ethylenically unsaturated group, and (C) a photopolymerization initiator.
A photosensitive resin composition containing.
[2] The photosensitive resin composition according to the above [1] or [2], wherein the component (A) contains a photopolymerizable compound having an acidic substituent together with the (A1) ethylenically unsaturated group.
[3] The photosensitive resin composition according to the above [1], wherein the content of the component (B) is 1 to 30% by mass based on the total amount of the resin components in the photosensitive resin composition.
[4] The photosensitive resin composition according to any one of the above [1] to [3], which further contains (D) an inorganic filler.
[5] The photosensitive resin composition according to any one of the above [1] to [4], which further contains (E) a thermosetting resin.
[6] The photosensitive resin composition according to the above [5], wherein the component (E) is an epoxy resin.
[7] A photosensitive resin composition for forming a photovia, which comprises the photosensitive resin composition according to any one of the above [1] to [6].
[8] A photosensitive resin composition for an interlayer insulating layer, which comprises the photosensitive resin composition according to any one of the above [1] to [6].
[9] A photosensitive resin film comprising the photosensitive resin composition according to any one of the above [1] to [6].
[10] A photosensitive resin film for an interlayer insulating layer, which comprises the photosensitive resin composition according to any one of the above [1] to [6].
[11] A multilayer printed wiring board including an interlayer insulating layer formed by using the photosensitive resin composition according to any one of the above [1] to [6].
[12] A multilayer printed wiring board including an interlayer insulating layer formed by using the photosensitive resin film according to the above [9].
[13] A semiconductor package in which a semiconductor element is mounted on the multilayer printed wiring board according to the above [11] or [12].
[14] A method for manufacturing a multilayer printed wiring board, which comprises the following steps (1) to (4).
Step (1): A step of laminating the photosensitive resin film according to the above [9] on one side or both sides of a circuit board.
Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in the step (1).
Step (3): A step of roughening the via and the interlayer insulating layer.
Step (4): A step of forming a circuit pattern on the interlayer insulating layer.

According to the present invention, there are provided a photosensitive resin composition having excellent via resolution, adhesive strength with plated copper, and insulation reliability, a photosensitive resin composition for forming photovia, and a photosensitive resin composition for an interlayer insulating layer. can do. Further, according to the present invention, there is provided a photosensitive resin film made of the photosensitive resin composition, a photosensitive resin film for an interlayer insulating layer, a multilayer printed wiring board and a semiconductor package, and a method for manufacturing the multilayer printed wiring board. be able to.

It is a schematic diagram which shows one aspect of the manufacturing process of the multilayer printed wiring board which uses the cured product of the photosensitive resin composition of this embodiment as at least one of a surface protective film and an interlayer insulating film.

In the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples. Further, in the present specification, the content of each component in the photosensitive resin composition is present in the photosensitive resin composition when a plurality of substances corresponding to each component are present, unless otherwise specified. It means the total content of the plurality of substances.
The present invention also includes aspects in which the items described in the present specification are arbitrarily combined.

In the present specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

[Photosensitive resin composition, photosensitive resin composition for forming photovia, and photosensitive resin composition for interlayer insulating layer]
The photosensitive resin composition according to one embodiment of the present invention (hereinafter, may be simply referred to as the present embodiment) is (A) a photopolymerizable compound having an ethylenically unsaturated group (provided that it has an epoxy group or an epoxy group). A photosensitive resin composition containing (excluding those having an oxetanyl group), (B) a compound having an epoxy group or an oxetanyl group and an ethylenically unsaturated group, and (C) a photopolymerization initiator.
In addition, in this specification, the said component may be referred to as a component (A), a component (B), a component (C), etc., respectively, and other components may be abbreviated in the same manner. As used herein, the term "resin component" means the total amount of components that do not contain an inorganic filler and a diluent that may be contained as needed, which will be described later. Further, the "solid content" is a non-volatile content excluding volatile substances such as water and a solvent contained in the photosensitive resin composition, and does not volatilize when the resin composition is dried. It shows the remaining components, and also includes liquid, starch syrup and wax-like substances at room temperature around 25 ° C.

Since the photosensitive resin composition is suitable for via formation by photolithography (also referred to as photo via formation), the present invention also relates to a photosensitive resin composition for forming photo vias comprising the photosensitive resin composition of the present embodiment. provide. Further, since the photosensitive resin composition is excellent in via resolution, adhesive strength with plated copper and insulation reliability, and is useful as an interlayer insulating layer of a multilayer printed wiring board, the present invention is carried out. Also provided is a photosensitive resin composition for an interlayer insulating layer comprising the photosensitive resin composition in the form. In the present specification, the term photosensitive resin composition also includes a photosensitive resin composition for forming a photovia and a photosensitive resin composition for an interlayer insulating layer.
The photosensitive resin composition of the present embodiment is useful as a negative photosensitive resin composition.
Hereinafter, each component that can be contained in the photosensitive resin composition will be described in detail.

<(A) Photopolymerizable compound having an ethylenically unsaturated group (excluding those having an epoxy group or an oxetanyl group)>
The photosensitive resin composition of the present embodiment contains a photopolymerizable compound having an ethylenically unsaturated group as a component (A) (excluding those having an epoxy group or an oxetanyl group).
The component (A) contains ethylene such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group, and a (meth) acryloyl group as functional groups exhibiting photopolymerizability. It is a compound having a functional group having a sex unsaturated bond. As the functional group exhibiting photopolymerizability, a (meth) acryloyl group is preferable.

In addition, "excluding those having an epoxy group or an oxetanyl group" for the component (A) means that the epoxy group or the oxetanyl group is intentionally used to distinguish the component (A) from the component (B) described later. It means that the compounds introduced into the above are excluded, and it does not mean that even those having an epoxy group or an oxetanyl group to the extent of impurities or unintentionally contained are excluded.

The components (A) include (Ai) a monofunctional vinyl monomer having one polymerizable ethylenically unsaturated group, (Aii) a bifunctional vinyl monomer having two polymerizable ethylenically unsaturated groups, and (Aiii). The embodiment containing at least one selected from the group consisting of polyfunctional vinyl monomers having at least three polymerizable ethylenically unsaturated groups 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 (Ai) monofunctional vinyl monomer include (meth) acrylic acid and (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, and (meth). Acrylic acid hydroxylethyl ester and the like can be mentioned. As the component (Ai), one type may be used alone, or two or more types may be used in combination.

((Aii) Bifunctional Vinyl Monomer)
Examples of the (Aii) bifunctional vinyl monomer include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, and 2,2-bis (4- (meth) acryloxy). Examples thereof include polyethoxypolypropoxyphenyl) propane and bisphenol A diglycidyl ether di (meth) acrylate. As the component (Aii), one type may be used alone, or two or more types may be used in combination.

((Aiii) Polyfunctional Vinyl Monomer)
(Aiii) Examples of the polyfunctional vinyl monomer include a (meth) acrylate compound having a skeleton derived from trimethylolpropane such as trimethylolpropane tri (meth) acrylate; trimethylolmethane tri (meth) acrylate, trimethylolmethanetetra ( A (meth) acrylate compound having a tetramethylolmethane-derived skeleton such as meta) acrylate; a (meth) acrylate compound having a pentaerythritol-derived skeleton such as pentaerythritol trimethylolpropane (meth) acrylate and pentaerythritol tetra (meth) acrylate; Pentaerythritol A (meth) acrylate compound having a dipentaerythritol-derived skeleton such as penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; having a dimethylolpropane-derived skeleton such as ditrimethylolpropane tetra (meth) acrylate. (Meta) acrylate compounds; examples thereof include (meth) acrylate compounds having a skeleton derived from diglycerin. Among these, from the viewpoint of improving chemical resistance after photocuring, a (meth) acrylate compound having a skeleton derived from dipentaerythritol is preferable, and dipentaerythritol penta (meth) acrylate is more preferable. As the component (Aiii), one type may be used alone, or two or more types may be used in combination.
Here, the above-mentioned "(meth) acrylate compound having a skeleton derived from XXX" (wherein, XXX is a compound name) means an esterified product of XXX and (meth) acrylic acid, and the esterified product. Also includes compounds modified with an alkyleneoxy group.

((A1) Photopolymerizable compound having an acidic substituent as well as an ethylenically unsaturated group)
Further, the component (A) is a photopolymerizable compound which can be alkaline-developed and has an acidic substituent as well as an ethylenically unsaturated group (A1) from the viewpoint of the resolution of vias and the adhesive strength with plated copper. Aspects including the above are also preferable. Here, examples of the acidic substituent include a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group, and the like, and among these, a carboxyl group is preferable.
As the component (A1), a compound obtained by modifying an epoxy resin (a1) with a vinyl group-containing organic acid (a2) from the viewpoint of alkali development and the resolution of vias and the adhesive strength with plated copper. [Hereinafter, it may be referred to as a component (A'). ], "(A1-1) Acid-modified vinyl group-containing epoxy derivative" obtained by reacting (a3) a saturated group or an unsaturated group-containing polybasic acid anhydride can be used.

-(A1) Epoxy resin-
(A1) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins and the like. Among these, a glycidyl ether type epoxy resin is preferable.

Further, the epoxy resin (a1) is classified into various epoxy resins according to the difference in the main skeleton, and each of the above types of epoxy resins is further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; bisphenol-based novolak-type epoxy resins such as bisphenol A novolak-type epoxy resin and bisphenol F novolak-type epoxy resin. Novolac type epoxy resin other than the bisphenol novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin; phenol aralkyl type epoxy resin; biphenyl aralkyl type epoxy resin; stillben type epoxy Resin; dicyclopentadiene type epoxy resin; naphthalene type epoxy resin, naphthol novolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphtholene ether type epoxy resin and other naphthalene skeleton-containing epoxy resin; biphenyl type epoxy resin It is classified into 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, the bisphenol-based novolac type epoxy resin is preferable, and the bisphenol F novolac type epoxy resin is more preferable from the viewpoint of reliability at the time of semiconductor mounting. (A1) As the epoxy resin, one type may be used alone, or two or more types may be used in combination.

The epoxy resin (a1) is also preferably an epoxy resin having a structural unit represented by the following general formula (I).

In the general formula (I), R ¹ represents a hydrogen atom or a methyl group, and Y ¹ independently represents a hydrogen atom or a glycidyl group. It is two R ¹ may be respectively identical or different. At least one of the two Y ¹ is a glycidyl group.
R ¹ is preferably a hydrogen atom from the viewpoint of via resolution and adhesive strength with plated copper. From the same viewpoint as this, it is preferable that Y ¹ is a glycidyl group.
The number of structural units in the epoxy resin (a1) having a structural unit represented by the general formula (I) is 1 or more, preferably 10 to 100, more preferably 15 to 80, and even more preferably. Is 15-70. When the number of structural units is within the above range, the adhesive strength, heat resistance and insulation reliability tend to be improved.
In the general formula (I), if R ¹ is a hydrogen atom and Y ¹ is a glycidyl group, the EXA-7376 series (manufactured by DIC Corporation, trade name) and R ¹ are both. Those having a methyl group and all of Y ¹ having a glycidyl group are commercially available as EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).

-(A2) Vinyl group-containing organic acid-
The vinyl group-containing organic acid (a2) is not particularly limited, but a vinyl group-containing monocarboxylic acid is preferable. Examples of the vinyl group-containing monocarboxylic acid include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-flufurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanoesteric acid and the like. Acrylic acid derivative; Semi-ester compound which is a reaction product of hydroxyl group-containing acrylate and dibasic acid anhydride; Vinyl group-containing monoglycidyl ether or reaction product of vinyl group-containing monoglycidyl ester and dibasic acid anhydride. Some semi-ester compounds; and the like.

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

Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the semiester compound which is an example of the component (a2) include hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate. , Hydroxypropyl methacrylate, Hydroxybutyl acrylate, Hydroxybutyl methacrylate, Polyethylene glycol monoacrylate, Polyethylene glycol monomethacrylate, Trimethylol propan diacrylate, Trimethylol propan dimethacrylate, Pentaerythritol triacrylate, Pentaerythritol trimethacrylate, Dipentaerythritol pentaacrylate , Pentaerythritol pentamethacrylate, glycidyl acrylate, glycidyl methacrylate and the like.

The dibasic acid anhydride used in the synthesis of the semi-ester compound may contain a saturated group or 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, phthalic anhydride and the like.

In the reaction between the component (a1) and the component (a2), it is preferable to react the component (a2) at a ratio of 0.6 to 1.05 equivalent to 1 equivalent of the epoxy group of the component (a1). The reaction may be carried out at a ratio of 0.8 to 1.0 equivalent. By reacting at such a ratio, the photopolymerizability tends to be improved, that is, the light sensitivity is increased, and the resolution of vias tends to be improved.

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

Further, it is preferable to use a catalyst to promote the reaction between the component (a1) and the component (a2). Examples of the catalyst include amine-based catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide and benzyltrimethylammonium iodide; triphenylphosphine. Benzyl-based catalysts such as, etc. Among these, a phosphine-based catalyst is 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, based on 100 parts by mass of the total of the components (a1) and (a2) from the viewpoint of obtaining an appropriate reaction rate. It is ~ 5 parts by mass, more preferably 0.1 to 2 parts by mass.

Further, it is preferable to use a polymerization inhibitor 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 a polymerization inhibitor is used, the amount used is preferably 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the component (a1) and the component (a2) from the viewpoint of improving the storage stability of the composition. It is 1 part by mass, more preferably 0.02 to 0.8 part by mass, and further preferably 0.1 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 even more preferably 90 to 110 ° C.

As described above, the component (A') formed by reacting the component (a1) and the component (a2) is formed by a cycloaddition reaction between the epoxy group of the component (a1) and the carboxyl group of the component (a2). It will have a hydroxyl group.

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

By further reacting the (A') component obtained above with the (a3) component containing a saturated or unsaturated group, the hydroxyl group of the (A') component (the hydroxyl group originally present in the (a1) component can also be obtained. (Including) and the acid anhydride group of the component (a3) are semi-esterified to obtain an (A1-1) acid-modified vinyl group-containing epoxy derivative.

In the reaction between the component (A') and the component (a3), for example, by reacting the component (a3) by 0.1 to 1.0 equivalent with respect to 1 equivalent of the hydroxyl group in the component (A'), ( A1-1) The acid value of the acid-modified vinyl group-containing epoxy derivative can be adjusted.
The acid value of the (A1-1) acid-modified vinyl group-containing epoxy derivative is preferably 20 to 150 mgKOH / g, more preferably 30 to 120 mgKOH / g, and even more preferably 40 to 90 mgKOH / g. When the acid value is 20 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution tends to be excellent, and when the acid value is 150 mgKOH / g or less, the electrical characteristics 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, still more preferably 70 to 100 ° C.

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

Further, as the component (A1), an epoxy-based polyurethane resin obtained by reacting the (a1) epoxy resin with a compound (a2) modified with a vinyl group-containing organic acid, that is, the component (A') and an isocyanate compound. (A1-3) can also be used. As the component (A1-3), one type may be used alone, or two or more types may be used in combination.

((A1) Molecular weight of a photopolymerizable compound having an acidic substituent as well as an ethylenically unsaturated group)
The weight average molecular weight (Mw) of the component (A1) is preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 18,000. Within this range, the adhesive strength with the plated copper, heat resistance and insulation reliability are improved. In particular, the weight average molecular weight (Mw) of the (A1-1) acid-modified vinyl group-containing epoxy derivative is preferably in the above range. Here, in the present specification, the weight average molecular weight is a value measured according to the following method.
<Measurement method of weight average molecular weight>
The weight average molecular weight was measured with the following GPC measuring device and measurement conditions, and the value converted using the standard polystyrene calibration curve was taken as the weight average molecular weight. In addition, a 5-sample set (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) was used as the standard polystyrene for preparing the calibration curve.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Tosoh Corporation Made by the company (measurement conditions)
Solvent: tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection volume: 20 μl

Examples of the acid-modified epoxy acrylate compound described above include CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185 and ZCR-1569H, ZCR-6000, ZCR-8000 (above, manufactured by Nippon Kayaku Co., Ltd., trade name), UE-9000, UE-EXP-2810PM, UE-EXP-3045 (above, manufactured by DIC Corporation, trade name) ) Etc. are commercially available.
Examples of photopolymerizable compounds having no carboxyl group include dipentaerythritol hexaacrylate and its similar structure, and commercially, KAYARAD DPHA, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA. -20, 30, KAYARAD DPCA-60, 120 (all manufactured by Nippon Kayaku Co., Ltd., product name), Aronix M400, Aronix M-402, Aronix M-408 (all manufactured by Toa Synthetic Co., Ltd., product name), Etc. are available. Trimethylolpropanetriethoxytriacrylate (SR-454, manufactured by Nippon Kayaku Co., Ltd., trade name) and the like are commercially available as polyfunctional photopolymerized compounds having three or more ethylenically unsaturated groups in one molecule. It is possible.
Examples of the photopolymerizable compound having a bisphenol A structure include FA-321M (manufactured by Hitachi Chemical Co., Ltd., trade name) or BPE, which is 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane. It is commercially available as -500 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) is BPE-1300 (new Nakamura Chemical Industry Co., Ltd.). It is commercially available as a product (trade name) manufactured by a corporation.

The content of the component (A) is not particularly limited, but is preferably 20 to 90% by mass based on the total amount of the resin component of the photosensitive resin composition from the viewpoint of heat resistance, electrical characteristics and chemical resistance. , More preferably 40 to 80% by mass, still more preferably 50 to 70% by mass.

The component (A) is not particularly limited, but from the viewpoint of photosensitive characteristics, it is preferable to use the component (A1) and the component (Aiii) in combination. In this case, the content ratio [(A1) / (Aiii)] (mass ratio) of the component (A1) and the component (Aiii) is preferably 1 to 20, more preferably 2 to 10, and even more preferably 3 to 6. is there.

<(B) Compound having an epoxy group or oxetanyl group and an ethylenically unsaturated group>
The photosensitive resin composition of the present embodiment contains a compound having an epoxy group or an oxetanyl group and an ethylenically unsaturated group as the component (B).
By containing the component (B), the photosensitive resin composition of the present embodiment has excellent via resolution, adhesive strength with plated copper, and insulation reliability. This is because the component (B) has an ethylenically unsaturated group capable of reacting with the component (A) and has an epoxy group or an oxetanyl group capable of reacting with an epoxy resin homopolymerized or optionally used. Therefore, it is considered that the component (B) serves as a cross-linking point of the three-dimensional network structure formed by curing the photosensitive resin composition, and the mechanical strength of the obtained cured product is improved.

The number of epoxy groups or oxetanyl groups (B) contained in one molecule is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.
The number of ethylenically unsaturated groups contained in one molecule of the component (B) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

Examples of the component (B) include (meth) acryloyl group-containing alicyclic epoxy resin, (meth) acryloyl group-containing bisphenol A type epoxy resin, (meth) acryloyl group-containing bisphenol F type epoxy resin, and (meth) acryloyl group. (Meta) acryloyl group-containing epoxy resin such as cresol novolac type epoxy resin, glycidyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate glycidyl ether; (3-ethyloxetane-3-yl) methyl ( Oxetanyl group-containing acrylates such as meta) acrylate and (3-ethyloxetane-3-yl) methyl (meth) acrylate; epoxy groups such as ethyloxetane methyl vinyl ether and cyclohexanedimethanol vinyl glycidyl ether or vinyl ethers having an oxetanyl group; Glycoluryl derivatives such as N, N'-diallyl-N'', N'''-diglycidyl glycol uryl (or 1,3-diallyl-4,6-diglycidyl glycol uryl); 1- (vinyl hydroxy) Examples thereof include methyl) -4- (glycidyl hydroxymethyl) cyclohexane.

As the component (B), a commercially available product may be used, and examples of the commercially available product include "NK ester EA-1010N", "EA-1010LC" and "EA-1010NT" which are epoxy group-containing acrylic resins. Shin-Nakamura Chemical Industry Co., Ltd.), ethyloxetane methyl vinyl ether "EOXTVE", cyclohexanedimethanol vinyl glycidyl ether "CHDMVG" (Maruzen Petrochemical Co., Ltd.), partially acrylated cresol novolac type Functional epoxy resins "ENA" and "ENC" (Kagawa Chemical Co., Ltd.), glycoluril derivatives "DAG-G" (manufactured by Shikoku Kasei Kogyo Co., Ltd.), and 4-hydroxybutyl acrylate glycidyl ether " 4HBAGE (manufactured by Nippon Kasei Co., Ltd.), (3-ethyloxetane-3-yl) methyl acrylate "OXE-10", (3-ethyloxetane-3-yl) methyl methacrylate "OXE-30" ( As mentioned above, (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like are available.

The content of the component (B) is not particularly limited, but is preferably 1 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 5 to 25% by mass, based on the total amount of the resin component of the photosensitive resin composition. It is 10 to 20% by mass. When the content of the component (B) is within the above range, the photosensitive resin composition is further excellent in the resolution of vias, the adhesive strength with plated copper, and the insulation reliability.

<(C) Photopolymerization Initiator>
The component (C) used in the present embodiment is not particularly limited as long as it can polymerize an ethylenically unsaturated group, and can be appropriately selected from commonly used photopolymerization initiators.
Examples of the component (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1. -Dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenones such as morpholino-1-propanone, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone, etc. Anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketal, benzyldimethylketal and other ketals; benzophenone, methylbenzophenone , 4,4'-Dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide and other benzophenones; 9-phenylacrine, 1,7-bis (9, Acrydins such as 9'-acrydinyl) heptane; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1,2-octandione-1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] etanone 1- (O-acetyloxime), 1-phenyl-1,2-propanedione Examples thereof include oxime esters such as -2- [O- (ethoxycarbonyl) oxime]. Among these, acetophenones and thioxanthones are preferable, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2,4-diethylthioxanthone are more preferable. Acetophenones have the advantage that they are less likely to volatilize and are less likely to be generated as outgas, and thioxanthones have the advantage that they can be photocured in the visible light region.
As the component (C), one type may be used alone, or two or more types may be used in combination. When two or more kinds are used in combination, it is preferable to use acetophenone and thioxanthone in combination, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2,4-diethylthioxanthone. It is more preferable to use in combination with.

The content of the component (C) is not particularly limited, but is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, based on the total amount of the resin component of the photosensitive resin composition. , More preferably 0.2 to 6% by mass, and particularly preferably 0.5 to 4% by mass. When the content of the component (C) is not more than the above lower limit value, there is a tendency to reduce the possibility that the exposed portion is eluted during development in the interlayer insulating layer formed by using the photosensitive resin composition. When it is not more than the above upper limit value, the heat resistance tends to be improved.

<(D) Inorganic filler>
The photosensitive resin composition of the present embodiment preferably contains an inorganic filler as the component (D). By containing the inorganic filler, low thermal expansion can be achieved, and the possibility of warpage is reduced. The thermosetting resin composition conventionally used as an interlayer insulating layer of a multilayer printed wiring board has been reduced in thermal expansion by containing an inorganic filler, but the photosensitive resin composition contains an inorganic filler. Then, since the inorganic filler causes light scattering and hinders development, it is difficult to add a large amount of the inorganic filler to achieve low thermal expansion. As described above, there is a new problem unique to the photosensitive resin composition in containing the inorganic filler, but it is assumed that the photosensitive resin composition of the present embodiment contains a large amount of the inorganic filler. However, the resolution of the via is high. Therefore, it is possible to achieve high resolution of vias as well as low thermal expansion.

Examples of the component (D) include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TIO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N). ₄ ), barium titanate (BaO · TiO ₂ ), barium carbonate (BaCO ₃ ), magnesium carbonate (MgCO ₃ ), aluminum hydroxide (Al (OH) ₃ ), magnesium hydroxide (Mg (OH) ₂ ), titanium Lead Acid Acid (PbO · TiO ₂ ), Lead Zirconate Tirate (PZT), Lead Zirconate Titanium (PLZT), Gallium Oxide (Ga ₂ O ₃ ), Spinel (MgO · Al ₂ O ₃ ), Murite (3Al) ₂ O ₃ · 2SiO _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. As the component (D), one type may be used alone, or two or more types may be used in combination. Among these, silica is preferable from the viewpoint of heat resistance and low thermal expansion.
As these inorganic fillers, those which have been surface-treated with alumina or an organic silane compound may be used from the viewpoint of improving the dispersibility in the photosensitive resin composition.

The average particle size of the component (D) is preferably 0.005 to 5 μm, more preferably 0.01 to 3 μm, and even more preferably 0.05 to 2 μm from the viewpoint of via resolution.
Here, the average particle size of the component (D) is the average particle size of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1,000 times (volume ratio) with methyl ethyl ketone, and then internationally using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5). In accordance with the standard ISO 13321, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle diameter at an integrated value of 50% (volume basis) in the particle size distribution is defined as the volume average particle diameter. Further, the component (D) 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 a solvent as described above. Later, it can be measured using the above-mentioned submicron particle analyzer.

When the photosensitive resin composition of the present embodiment contains the component (D), the content thereof is not particularly limited, but is preferably 10 to 80 based on the total solid content of the photosensitive resin composition. It is by mass, more preferably 12 to 70% by mass, still more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass. When the content of the component (D) is within the above range, the mechanical strength, heat resistance, resolution of vias, and the like can be improved. However, depending on the desired performance, the photosensitive resin composition of the present embodiment may not contain the component (D).

<(E) Thermosetting resin>
The photosensitive resin composition of the present embodiment may further contain (E) a thermosetting resin in addition to the above components (A) to (D). (E) By containing the thermosetting resin, the heat resistance is improved in addition to the improvement of the adhesive strength and the insulation reliability with the plated copper.
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, and silicone. Examples thereof include resins, triazine resins, and melamine resins. Further, the present invention is not particularly limited to these, and a known thermosetting resin can be used. Among these, epoxy resin is preferable. The epoxy resin does not contain the components (A) and (B), and in that respect, it can be said that the epoxy resin used as the component (E) does not have an ethylenically unsaturated group. In addition, a substance having an epoxy group after satisfying the above conditions is included in the component (E).
As the component (E), one type may be used alone, or two or more types may be used in combination.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins and the like. Among these, a glycidyl ether type epoxy resin is preferable.

The epoxy resin of the component (E) is classified into various epoxy resins according to the difference in the main skeleton, and the epoxy resins of each of the above types are further classified as follows. Specifically, bisphenol-based epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and bisphenol S-type epoxy resin; bisphenol-based novolak-type epoxy resins such as bisphenol A novolak-type epoxy resin and bisphenol F novolak-type epoxy resin. Novolac type epoxy resin other than the bisphenol novolac type epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin; phenol aralkyl type epoxy resin; biphenyl aralkyl type epoxy resin; stillben type epoxy Resin; dicyclopentadiene type epoxy resin; naphthalene type epoxy resin, naphthol novolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphtholene ether type epoxy resin and other naphthalene skeleton-containing 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; and the like.

Among these, bisphenol-based epoxy resin, naphthol-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, and naphthylene ether-type epoxy resin are particularly selected from the viewpoints of heat resistance, insulation reliability, and adhesive strength with plated copper. Preferably, a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are more preferable, and a bisphenol F type epoxy resin is further preferable.
Commercially available products can also be used for these, for example, bisphenol A type epoxy resin (“jER828EL”, “YL980” manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Co., Ltd.). ”), Naphthalene type epoxy resin (“HP4032D”, “HP4710” manufactured by DIC Co., Ltd.), Naphthalene skeleton-containing polyfunctional epoxy resin (“NC7000” manufactured by Nippon Kayaku Co., Ltd.), Naftor type epoxy resin (Nippon Steel & Sumitomo Metal Chemical) "ESN-475V" manufactured by Nippon Kayaku Co., Ltd.), epoxy resin with biphenyl structure ("NC3000H", "NC3500" manufactured by Nippon Kayaku Co., Ltd.), "YX4000HK", "YL6121" manufactured by Mitsubishi Chemical Co., Ltd.), anthracene type epoxy resin ("YX8800" manufactured by Mitsubishi Chemical Co., Ltd.), glycerol type epoxy resin ("ZX1542" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), naphthylene ether type epoxy resin ("EXA7311-G4" manufactured by DIC Co., Ltd.) and the like. ..

As the epoxy resin of the component (E), epoxy-modified polybutadiene (hereinafter, also referred to as “epoxydated polybutadiene”) can be used in addition to the above examples. In particular, as the component (E), from the viewpoint of preventing cracking during transportation of the printed wiring board, it is preferable to use an aromatic epoxy resin that is solid at room temperature and an epoxy resin that is liquid at room temperature in combination. It is preferable to use the epoxy resin exemplified as preferable (aromatic epoxy resin solid at room temperature) and epoxy-modified polybutadiene (epoxy resin liquid at room temperature) in combination. In this case, the content ratio of both to be used in combination (aromatic epoxy resin solid at room temperature / epoxy resin liquid at room temperature) is preferably 1 to 10 and more preferably 2 to 5 in terms of mass ratio.

The epoxy-modified polybutadiene preferably has a hydroxyl group at the end of the molecule, more preferably has a hydroxyl group at both ends of the molecule, and further preferably has a hydroxyl group only at both ends of the molecule. 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 even more preferably 2.
The epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (E-1) from the viewpoint of adhesive strength with plated copper, heat resistance, coefficient of thermal expansion and flexibility.

(In the above formula (E-1), a, b and c represent the ratio of the structural units in parentheses, respectively, where a is 0.05 to 0.40 and b is 0.02 to 0.30. , C is 0.30 to 0.80, and further satisfies a + b + c = 1.00 and (a + c)> b. Y represents the number of structural units in square brackets and is an integer of 10 to 250. is there.)

In the general formula (E-1), the order of joining each structural unit in the square brackets is random. That is, the structural unit shown on the left, the structural unit shown in the center, and the structural unit shown on the right may be interchanged, and they are referred to as (a), (b), and (c), respectively. When expressed 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)-(b) )-(C)-]-,-[(c)-(b)-(c)]-[(b)-(a)-(a)-]-, and so on.
From the viewpoint of adhesive strength with plated copper, heat resistance, coefficient of thermal expansion and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0. It is 40 to 0.80. From the same viewpoint as this, y is preferably an integer of 30 to 180.

In the general formula (E-1), as a commercially available product of epoxidized polybutadiene having integers of a = 0.20, b = 0.20, c = 0.60, and y = 10 to 250, "Epolide (Epolide (Epolide) Registered trademark) PB3600 ”(manufactured by Daicel Corporation) and the like.

The content of the component (E) is not particularly limited, but is preferably 5 to 70% by mass, more preferably 10 to 50% by mass, still more preferably, based on the total amount of the resin component of the photosensitive resin composition. It is 12 to 40% by mass, particularly preferably 15 to 30% by mass. When the content of the component (E) is at least the above lower limit value, sufficient cross-linking of the photosensitive resin composition is obtained, and the adhesive strength with the plated copper and the insulation reliability tend to be improved. On the other hand, when it is not more than the above upper limit value, the resolution of the via tends to be good.

<(F) Pigment>
The photosensitive resin composition of the present embodiment may contain a pigment as the component (F) for the purpose of adjusting the photosensitive characteristics. Examples of the component (F) include phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like.
When the photosensitive resin composition of the present embodiment contains the component (F), the content thereof is preferably 0.01 to 5% by mass, more preferably 0, based on the total amount of the resin component of the photosensitive resin composition. It is .03 to 3% by mass, more preferably 0.05 to 2% by mass.

<(G) Epoxy resin curing agent>
An epoxy resin curing agent can be used in combination with the photosensitive resin composition of the present embodiment for the purpose of further improving various properties such as heat resistance, adhesion, and chemical resistance of the obtained insulating layer.
Specific examples of the component (G) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methyl-5-. Imidazole derivatives such as hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylene diamine, diaminodiphenyl sulfone, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide. These organic acid salts and / or epoxy adducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xysilyl-S-triazine Triazine derivatives such as: trimethylamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholin, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), Tertiary amines such as tetramethylguanidine and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolac and alkylphenol novolac; organics such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine Hosphins; phosphonium salts such as tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide, hexadecyltributylphosnium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; Basic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate and the like.
When the photosensitive resin composition of the present embodiment contains the component (G), the content thereof is preferably 0.01 to 20% by mass, more preferably 0, based on the total amount of the resin component of the photosensitive resin composition. .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 ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether and dipropylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, carbitol acetate; octane, decane And other aliphatic hydrocarbons; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha can be mentioned. As the diluent, one type may be used alone, or two or more types may be used in combination.

The content of the diluent is 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. It may be selected as appropriate. By adjusting the amount of the diluent used in this way, the coatability of the photosensitive resin composition is improved, and a higher-definition pattern can be formed.

<Other additives>
The photosensitive resin composition of the present embodiment may contain, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; a thickener such as Benton, montmorillonite; a silicone defoamer, Various known and commonly used additives such as defoaming agents such as fluorine-based defoaming agents and vinyl resin-based defoaming agents; various elastomers; and silane coupling agents; can be contained. Furthermore, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, phosphate compounds of antimony compounds and phosphorus compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters 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 as a liquid or as a film.
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, from the viewpoint of more easily forming the photosensitive layer, a printing method or a spin coating method may be appropriately selected.
When used as a film, for example, it can be used in the form of a photosensitive resin film described later. In this case, a photosensitive layer having a desired thickness is formed by laminating it on a carrier film using a laminator or the like. be able to. It is preferable to use it in the form of a film because the manufacturing efficiency of the multilayer printed wiring board is high.

[Photosensitive resin film, photosensitive resin film for interlayer insulation layer]
The photosensitive resin film of the present embodiment is a photosensitive layer that will later become an interlayer insulating layer, and is made of the photosensitive resin composition of the present embodiment. A mode in which a photosensitive resin film is provided on the carrier film may be used.
The thickness (thickness after drying) of the photosensitive resin film (photosensitive layer) is not particularly limited, but is preferably 1 to 100 μm, more preferably 3 to 50 μm, from the viewpoint of reducing the thickness of the multilayer printed wiring board. , More preferably 5 to 40 μm.

The photosensitive resin film of the present embodiment is, for example, a known coating of the photosensitive resin composition of the present embodiment on a carrier film, such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater. It is obtained by forming a photosensitive layer to be an interlayer insulating layer later by applying 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, but is preferably 5 to 60 μm, more preferably 15 to 45 μm.

Further, 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 such as polyethylene or polypropylene can be used. Further, a polymer film similar to the carrier film described above 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 even more preferably 80 to 100 ° C. The drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes. The content of the 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 avoiding diffusion of the diluent in the manufacturing process of the multilayer printed wiring board. 1, 1% by mass or less is more preferable.

The photosensitive resin film of the present embodiment is excellent in resolution of vias, adhesive strength with plated copper, and insulation reliability, and is therefore suitable as an interlayer insulating layer of a multilayer printed wiring board. That is, the present invention also provides a photosensitive resin film for an interlayer insulating layer made of the photosensitive resin composition of the present embodiment. The photosensitive resin film for the interlayer insulating layer can also be referred to as an interlayer insulating photosensitive film.

[Multilayer printed wiring board and its manufacturing method]
The multilayer printed wiring board of the present embodiment contains an interlayer insulating layer formed by using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment. The method for producing the multilayer printed wiring board of the present embodiment is not particularly limited 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 of manufacturing a multilayer printed wiring board using the photosensitive resin film (photosensitive resin film for interlayer insulating layer) of the present embodiment will be described as appropriate with reference to FIG.
The multilayer printed wiring board 100A can be manufactured, for example, by a manufacturing method including the following steps (1) to (4).
Step (1): A step of laminating the photosensitive resin film of the present embodiment on one side or both sides of a circuit board [hereinafter, referred to as a laminating step (1)].
Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in the step (1) [hereinafter, referred to as a photovia forming step (2)].
Step (3): A step of roughening the via and the interlayer insulating layer [hereinafter, referred to as a roughening treatment step (3)].
Step (4): A step of forming a circuit pattern on the interlayer insulating layer [hereinafter, referred to as a circuit pattern forming step (4)].

(Laminating process (1))
In the laminating step (1), the photosensitive resin film (photosensitive resin film for interlayer insulating layer) of the present embodiment is laminated on one side or both sides of a circuit board (board 101 having a circuit pattern 102) using a vacuum laminator. It is a process. Vacuum laminators include vacuum applicators manufactured by Nichigo Morton Co., Ltd., vacuum pressurized laminators manufactured by Meiki Co., Ltd., roll-type dry coaters manufactured by Hitachi, Ltd., and vacuum laminators manufactured by Hitachi Kasei Electronics Co., Ltd. Can be mentioned.

When a protective film is provided on the photosensitive resin film, after peeling or removing the protective film, the photosensitive resin film is pressed and laminated on the circuit board while being pressurized and heated so as to be in contact with the circuit board. can do.
In the laminate, for example, the photosensitive resin film and the circuit board are preheated as necessary, and then the crimping temperature is 70 to 130 ° C., the crimping 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. Further, the laminating method may be a batch method or a continuous method using a roll.
Finally, the photosensitive resin film laminated on the circuit board (hereinafter, may be referred to as a photosensitive layer) is cooled to around room temperature to form an interlayer insulating layer 103. The carrier film may be peeled off here, or may be peeled off after exposure as described later.

(Photovia forming 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 exposure, the portion irradiated with the active light is photocured to form a pattern. The exposure method is not particularly limited, and for example, a method of irradiating an active light beam in an image form through a negative or positive mask pattern called artwork (mask exposure method) may be adopted, or LDI (Laser Direct Imaging) may be adopted. A method of irradiating an active light beam in an image shape 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 active light beam. Specifically, as the light source, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, a gas laser such as an argon laser; a solid-state laser such as a YAG laser; an ultraviolet ray or a visible light such as a semiconductor laser is effectively emitted. Things; etc. The amount of exposure is appropriately selected depending on the light source used, the thickness of the photosensitive layer, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, when the thickness of the photosensitive layer is 1 to 100 μm, it is usually about 10 to 1,000 J / m ^2. Is preferable, and 15 to 500 J / m ² is more preferable.

In development, the uncured portion of the photosensitive layer is removed from the substrate, so that an interlayer insulating layer made of a photocured cured product is formed on the substrate.
If a carrier film is present on the photosensitive layer, the carrier film is removed, and then the unexposed portion is removed (developed). There are two types of development methods, wet development and dry development, and either of them may be adopted. However, wet development is widely used, and wet development can also be adopted in this embodiment.
In the case of wet development, development is carried out by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dip method, a battle method, a spray method, brushing, slapping, scraping, rocking immersion, and the like. Among these, 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 carried out by one kind of method, but may be carried out by combining two or more kinds of methods.
The composition of the developing solution is appropriately selected according to the composition of the photosensitive resin composition. Examples thereof include an alkaline aqueous solution, an aqueous developer and an organic solvent developer, and among these, an alkaline aqueous solution is preferable.

In the photovia forming step (2), after exposure and development, a 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. The interlayer insulating layer may be further cured by, if necessary, post-thermal curing at a temperature of (preferably 120-200 ° C.), and it is preferable to do so.
As described above, the interlayer insulating layer having the via 104 is formed. The shape of the via is not particularly limited, and the cross-sectional shape includes, for example, a quadrangle, an inverted trapezoid (the upper side is longer than the lower side), and the shape viewed from the front (the direction in which the bottom of the via can be seen) is a circle. , Squares, etc. In the formation of vias by the photolithography method in the present embodiment, vias having an inverted trapezoidal cross-sectional shape (the upper side is longer than the lower side) can be formed, and in this case, the plating copper has a high tendency to attach to the via wall surface. Is preferable.

The size (diameter) of the vias formed by this step can be less than 40 μm, and further can be 35 μm or less or 30 μm or less, which is smaller than the size of the vias produced by laser processing. can do. The lower limit of the size (diameter) of the via formed by 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 by this step is not limited to less than 40 μm, and may be arbitrarily selected in the range of, for example, 15 to 300 μm.

(Roughening process (3))
In the roughening treatment step (3), the surfaces of the via and the interlayer insulating layer are roughened with a roughening liquid. If smear is generated in the photovia forming step (2), the smear may be removed by the roughening solution. The roughening treatment and the removal of smear can be performed at the same time.
Examples of the roughening solution include chromium / sulfuric acid roughening solution, alkaline permanganate roughening solution (for example, sodium permanganate roughening solution, etc.), sodium fluoride / chromium / sulfuric acid roughening solution, and the like.
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 formation of the circuit pattern is preferably carried out by a semi-additive process from the viewpoint of forming fine wiring. The semi-additive process forms the circuit pattern and conducts the vias.
In the semi-additive process, first, after the roughening treatment step (3), the via bottom, the via wall surface, and the entire surface of the interlayer insulating layer are subjected to electroless copper plating treatment after using a palladium catalyst or the like to perform the seed layer 105. To form. The seed layer is for forming a 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. It is not necessary to increase the amount of etching at the time, and there is a tendency that damage to the wiring during etching can be suppressed.

The electroless copper plating treatment is performed by depositing metallic copper on the surfaces of vias and the interlayer insulating layer by the reaction of copper ions and a reducing agent.
The electroless plating treatment method and the electroless 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, and the catalyst of the catalyst. The primary particle size is preferably 10 nm or less. Further, the plating composition of the electroless plating treatment step preferably contains hypophosphorous acid as a reducing agent.
Commercially available products can be used as the electroless copper plating solution. Examples of commercially available products include "MSK-DK" manufactured by Atotech Japan Co., Ltd. and "Sulcup (registered trademark) PEA series" manufactured by Uemura Kogyo Co., Ltd. Can be mentioned.

After performing the electroless copper plating treatment, the dry film resist is thermocompression bonded on 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, the "Fotech" series manufactured by Hitachi Chemical Co., Ltd. or the like is used.
After thermocompression bonding of the dry film resist, for example, the dry film resist is exposed through a mask on which a desired wiring pattern is drawn. The exposure can be performed with the same equipment and light source as those that can be used for forming vias on the photosensitive resin film. After the exposure, the carrier film on the dry film resist is peeled off and developed with an alkaline aqueous solution to remove the unexposed portion to form the resist pattern 106. After that, if necessary, the work of removing the development residue of the dry film resist may be performed using plasma or the like.
After development, electrolytic copper plating is performed to form and via fill the copper circuit layer 107.

After electrolytic copper plating, the dry film resist is peeled off using an alkaline aqueous solution or an amine-based release agent. After peeling off 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. After flash etching, if necessary, remove palladium or the like adhering to the portion between the wirings. The removal of palladium can preferably be carried out using an acidic solution such as nitric acid or hydrochloric acid.

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

The method for manufacturing a multilayer printed wiring board for forming vias using the photosensitive resin composition of the present embodiment has been described above, but the photosensitive resin composition of the present embodiment is excellent in pattern resolution. Therefore, for example, it is also suitable for forming a cavity for incorporating a chip, a passive element, or the like. The cavity is preferably formed by, for example, in the above description of the multilayer printed wiring board, the drawing pattern when the photosensitive resin film is exposed to form the pattern can form a desired cavity. Can be done.

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

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 compositions obtained in each example were evaluated by the methods shown below.

[1. Evaluation of via resolution]
(1) Preparation of Laminate for Evaluation The copper foil surface of a printed wiring board substrate (manufactured by Hitachi Kasei Co., Ltd., trade name "MCL-E-679") in which a 12 μm thick copper foil is laminated on a glass epoxy base material is used. After treatment with a roughening pretreatment liquid (manufactured by MEC Co., Ltd., trade name "CZ-8100"), it was washed with water and dried to obtain a roughened pretreated printed wiring board substrate. Next, the protective film was 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 was removed from the substrate for the printed wiring board which had been roughened and pretreated. After placing the film so as to come into contact with the copper foil of the above, a laminating treatment was performed using a press-type vacuum laminator (manufactured by Meiki Co., Ltd., trade name "MVLP-500"). The laminating conditions were a press hot 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 crimping pressure of 0.4 MPa. After the laminating treatment, the film was left at room temperature for 1 hour or more to obtain an evaluation laminate in which a photosensitive resin film and a carrier film were laminated in this order on a copper foil surface of a 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 placed and a direct imaging exposure device "DXP" using an ultra-high pressure mercury lamp as a light source. Exposure was performed using "-3512" (manufactured by ORC Manufacturing Co., Ltd.). As the exposure pattern, a pattern in which dots were arranged in a grid pattern (dot diameter: distance between dot centers = 1: 2) was used. The diameter of the dots was changed in the range of φ30 to 100 μm in increments of 5 μm.
After the exposure, the mixture was left at room temperature for 30 minutes, and then the photosensitive resin composition in the unexposed portion was spray-developed for 60 seconds using a 1% by mass sodium carbonate aqueous solution at 30 ° C. After development, the amount of exposure energy at which the number of remaining glossy steps of the 41-step step tablet was 7.0 was defined as the sensitivity (unit: mJ / cm ² ) of the photosensitive resin film. Using the pattern exposed with this sensitivity, the resolution of the vias provided on the photosensitive resin film was evaluated according to the following evaluation criteria.
(3) Evaluation of resolution In the evaluation of resolution, exposure is performed with an exposure energy amount such that the number of steps is 7.0, then spray development is performed, and then a via pattern is observed using an optical microscope according to the following criteria. evaluated. The following "opening" state refers to a state in which the copper foil of the substrate for the printed wiring board can be confirmed when observing the via portion of the dot pattern using an optical microscope. The judgment of "A" shows good characteristics.
A: The φ60 μm via portion of the dot pattern is open.
C: The φ60 μm via portion of the dot pattern is not open.

[2. Evaluation of adhesive strength (peeling strength) with plated copper]
(1) Preparation of laminate for evaluation and sensitivity measurement of photosensitive resin film [1. Evaluation of resolution] The exposure machine used in steps (1) and (2) was a parallel light exposure machine using an ultra-high pressure mercury lamp as a light source (manufactured by ORC Manufacturing Co., Ltd., trade name "EXM-1201"). ), Except for the above [1. Perform the same operation as in steps (1) and (2) of [Evaluation of resolution] to obtain the amount of exposure energy at which the number of remaining gloss steps is 10.0, and use this as the sensitivity (unit: unit;) of the photosensitive resin film. It was set to mJ / cm ² ).
(2) Exposure step and development step Next, the carrier film of the evaluation laminate is peeled off, and the surface of the exposed photosensitive resin film is exposed to the entire surface with the exposure energy amount obtained above, and the photosensitive resin is exposed. An insulating layer formed by curing the film was formed.
(3) Post-cure treatment Next, post-UV cure is performed at a conveyor speed of ² J / cm ² with a high-pressure mercury lamp irradiation type UV conveyor device (manufactured by ORC Manufacturing Co., Ltd.), and then hot air circulation type. Post-heat curing was performed at 170 ° C. for 1 hour using a dryer (manufactured by Futaba Kagaku Co., Ltd.).
(4) Roughing Treatment The evaluation laminate after the post-cure treatment is treated with the swelling liquid "Swelling Dip Securigant P" at 70 ° C. for 5 minutes, and then the roughening liquid "Dosing Securigant P500J". Was treated at 70 ° C. for 10 minutes, and further treated with a neutralizing solution “reduction conditioner securigant P500” at 40 ° C. for 5 minutes to perform roughening treatment. The swelling solution, the roughening solution, and the neutralizing solution were all manufactured by Atotech Japan Co., Ltd.
(5) Plating treatment The electroless plating solution "Prigant MSK-DK" (manufactured by Atotech Japan Co., Ltd.) is used for the evaluation laminate after the roughening treatment at 30 ° C. for 20 minutes. Then, using the electroplating solution "Capallaside HL" (manufactured by Atotech Japan Co., Ltd.), the electroplating treatment was performed at 24 ° C. and 2 A / dm ² for 1 hour to form a plated copper layer on the insulating layer. An evaluation substrate for measuring the adhesive strength with plated copper was prepared. The thickness of the plated copper formed by the plating treatment was 25 μm.
(6) Measurement of Adhesive Strength (Peel Strength) with Plated Copper The adhesive strength with plated copper is measured by measuring the vertical peeling strength at 23 ° C. in accordance with JIS C6481 (1996). The evaluation was based on the following criteria.
A: 0.40 kN / m or more B: 0.35 kN / m or more, less than 0.40 kN / m C: less than 0.35 kN / m

[3. Evaluation of insulation reliability (HAST resistance)]
MSAP (Modified Semi-Adaptive Process) method using a printed wiring board substrate (manufactured by Hitachi Kasei Co., Ltd., trade name: MCL-E-700G (R)) in which a copper foil having a thickness of 18 μm is laminated on a glass epoxy base material. A comb-shaped electrode having a line / space of 12 μm / 12 μm was prepared in 1 and used as an evaluation substrate.
On this evaluation board, the above [1. An interlayer insulating layer made of a photosensitive resin film is formed in the same manner as in [Evaluation of resolution], and then [2. Evaluation of adhesive strength (peel strength) with plated copper], plated copper was formed. Then, an electrode having a diameter of 6 mm was formed by etching. It was then exposed under 130 ° C., 85% RH, 6 V conditions for 200 hours. The resistance value between the electrodes was measured, and the time when the resistance value became ^10-6 Ω or less was defined as the copper migration occurrence time, and the insulation reliability (HAST resistance) between the layers was evaluated according to the following evaluation criteria.
A: No copper migration occurs after 200 hours.
B: Copper migration occurrence time is 100 hours or more and 200 hours or less.
C: Copper migration occurs for less than 100 hours.

[Manufacture of acid-modified vinyl group-containing epoxy derivatives]
Synthesis example 1
(Synthesis of acid-modified epoxy acrylate resin (A-1))
Bisphenol F novolak type epoxy resin (manufactured by DIC Corporation, trade name "EXA-7376") 350 parts by mass, 70 parts by mass of acrylic acid, 0.5 parts by mass of methylhydroquinone, 120 parts by mass of carbitol acetate were charged into the reaction vessel. The reaction was carried out by heating to 90 ° C. and stirring. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. and reacted until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride and 85 parts by mass of carbitol acetate were added, heated to 80 ° C., reacted for about 6 hours, and then cooled to have a solid content concentration of 73% by mass (). A) A solution of an acid-modified epoxy acrylate resin (A-1) as a component was obtained.

<Examples 1 to 3 and Comparative Examples 1 to 2>
(Preparation of photosensitive resin composition)
The compositions were 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 Co., Ltd., trade name) having a thickness of 25 μm was used as a carrier film, and the photosensitive resin composition prepared in each example was placed on the carrier film to a thickness of 25 μm after drying. And dried at 100 ° C. for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Subsequently, a biaxially stretched polypropylene film (MA-411, manufactured by Oji Ftex Co., Ltd., trade name) is placed on the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film. It was bonded as a protective film to prepare a carrier film and a photosensitive resin film to which the protective film was bonded.
Each evaluation was performed according to the above method using the produced photosensitive resin film. The results are shown in Table 1.

The components used in each example are as follows.
[(A) component]
-Acid-modified epoxy acrylate resin (A-1): Acid-modified epoxy acrylate resin (A-1) prepared in Synthesis Example 1.
-Dipentaerythritol pentaacrylate [(B) component]
Epoxy group-containing acrylic resin: (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trade name "EA-1010LC") (meth) acryloyl group having one epoxy group and one ethylenically unsaturated group in one molecule. Containing bisphenol A type epoxy resin)
-N, N'-diallyl-N ", N'"-diglycidyl glycol uryl (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name "DAG-G", two epoxy groups in one molecule and ethylenically non-ethylous Compound having two saturated groups)
[Component (C)]
-2-Methyl- [4- (methylthio) phenyl] morpholino-1-propanone, acetophenone-2,4-diethylthioxanthone, thioxanthone [(D) component]
-Spherical silica (average particle size 0.5 μm)
[(E) component]
-Epoxy resin: (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., product name "YDF-8170C")
-Epoxyted polybutadiene: (manufactured by Daicel Chemical Co., Ltd., trade name "PB3600")
[(F) component]
・ Phthalocyanine pigment [(G) component]
·melamine

As is clear from the results shown in Table 1, the photosensitive resin films (photosensitive resin compositions) of Examples 1 to 3 are plated copper formed on the insulating material without impairing the excellent resolution of vias. It was confirmed that it has excellent peel strength and, in addition, excellent insulation reliability (HAST resistance).

100A Multi-layer printed wiring board 102 Circuit pattern 103 Interlayer insulation layer 104 Via (via hole)
105 Seed layer 106 Resist pattern 107 Copper circuit layer 108 Solder resist layer

Claims (14)

(A) Photopolymerizable compounds having an ethylenically unsaturated group (excluding those having an epoxy group or an oxetanyl group),
(B) A compound having an epoxy group or an oxetanyl group and an ethylenically unsaturated group, and (C) a photopolymerization initiator.
A photosensitive resin composition containing. The photosensitive resin composition according to claim 1, wherein the component (A) contains a photopolymerizable compound having an acidic substituent as well as an ethylenically unsaturated group (A1). The photosensitive resin composition according to claim 1 or 2, wherein the content of the component (B) is 1 to 30% by mass based on the total amount of the resin component in the photosensitive resin composition. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) an inorganic filler. The photosensitive resin composition according to any one of claims 1 to 4, further containing (E) a thermosetting resin. The photosensitive resin composition according to claim 5, wherein the component (E) is an epoxy resin. A photosensitive resin composition for forming a photovia, which comprises the photosensitive resin composition according to any one of claims 1 to 6. A photosensitive resin composition for an interlayer insulating layer, which comprises the photosensitive resin composition according to any one of claims 1 to 6. A photosensitive resin film comprising the photosensitive resin composition according to any one of claims 1 to 6. A photosensitive resin film for an interlayer insulating layer, which comprises the photosensitive resin composition according to any one of claims 1 to 6. A multilayer printed wiring board containing an interlayer insulating layer formed by using the photosensitive resin composition according to any one of claims 1 to 6. A multilayer printed wiring board including an interlayer insulating layer formed by using the photosensitive resin film according to claim 9. A semiconductor package in which a semiconductor element is mounted on a multilayer printed wiring board according to claim 11 or 12. A method for manufacturing a multilayer printed wiring board, which comprises the following steps (1) to (4).
Step (1): A step of laminating the photosensitive resin film according to claim 9 on one side or both sides of a circuit board.
Step (2): A step of forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in the step (1).
Step (3): A step of roughening the via and the interlayer insulating layer.
Step (4): A step of forming a circuit pattern on the interlayer insulating layer.