阅读说明：本技术 感光性树脂组合物、感光性树脂膜、印刷配线板和半导体封装体、以及印刷配线板的制造方法 (Photosensitive resin composition, photosensitive resin film, printed wiring board, semiconductor package, and method for producing printed wiring board ) 是由 中村彰宏 高濑有司 泽本飒人 铃木庆一 野本周司 冈出翔太 于 2020-05-25 设计创作，主要内容包括：本发明涉及一种感光性树脂组合物、使用了该感光性树脂组合物的感光性树脂膜、印刷配线板及其制造方法、以及半导体封装体,该感光性树脂组合物含有(A)具有乙烯性不饱和基和酸性取代基的光聚合性化合物、以及(B)光聚合引发剂,该感光性树脂组合物所含的成分中的至少1种为包含二环戊二烯骨架的成分。(The present invention relates to a photosensitive resin composition containing (a) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, and (B) a photopolymerization initiator, wherein at least 1 of the components contained in the photosensitive resin composition is a component containing a dicyclopentadiene skeleton, a photosensitive resin film using the photosensitive resin composition, a printed wiring board, a method for producing the printed wiring board, and a semiconductor package.)

1. A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and (B) a photopolymerization initiator,

at least 1 of the components contained in the photosensitive resin composition is a component containing a dicyclopentadiene skeleton.

2. The photosensitive resin composition according to claim 1, wherein the component containing a dicyclopentadiene skeleton contains a structure represented by the following general formula (X-1),

[ solution 1]

In the formula, R^X1And R^X2Each independently is a divalent radical having 1 or more groups selected from the group consisting of alkylene, arylene, and oxy, and is a binding site to other structures.

3. The photosensitive resin composition according to claim 1 or 2, wherein the total mass of the dicyclopentadiene skeleton contained in the photosensitive resin composition is 5% by mass or more relative to the total solid content of the components contained in the photosensitive resin composition.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent is an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by reacting (c) a saturated or unsaturated group-containing polybasic acid anhydride with a resin (A') obtained by reacting (a) an epoxy resin with (b) an ethylenically unsaturated group-containing organic acid.

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent comprises a dicyclopentadiene skeleton.

6. The photosensitive resin composition according to claim 4, wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent comprises:

(A1) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using an epoxy resin having a dicyclopentadiene skeleton as the epoxy resin (a); and

(A2) the acid-modified ethylenically unsaturated group-containing epoxy derivative is obtained by using 1 or more selected from the group consisting of a novolak epoxy resin, a bisphenol epoxy resin and a triphenolmethane epoxy resin as the epoxy resin (a).

7. The photosensitive resin composition according to any one of claims 1 to 6, further comprising (C) a photopolymerizable compound having no acidic substituent.

8. The photosensitive resin composition according to claim 7, wherein the photopolymerizable compound (C) having no acidic substituent is a polyfunctional monomer having 3 or more ethylenically unsaturated groups.

9. The photosensitive resin composition according to claim 7 or 8, wherein the photopolymerizable compound (C) having no acidic substituent comprises a dicyclopentadiene skeleton.

10. The photosensitive resin composition according to any one of claims 1 to 9, further comprising (D) a thermosetting resin.

11. The photosensitive resin composition according to any one of claims 1 to 10, further comprising (E) a pigment.

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

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

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

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

16. A printed wiring board comprising a surface protective film or an interlayer insulating layer formed by using the photosensitive resin composition according to any one of claims 1 to 12 or the photosensitive resin film according to claim 15.

17. A semiconductor package comprising a semiconductor element mounted on the printed wiring board of claim 16.

18. A method for manufacturing a printed wiring board, comprising the steps of: a step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 12 or the photosensitive resin film according to claim 15; a step of forming a resin pattern using the photosensitive layer; and forming at least one of a surface protective film and an interlayer insulating layer by curing the resin pattern.

Technical Field

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

Background

In recent years, with the high performance (miniaturization, weight reduction, and multi-functionalization) of electronic devices, high Integration of semiconductor components such as LSI (Large Scale Integration) and chips has been advanced. With this, the form of semiconductor components is rapidly changing toward multi-pin and small-sized semiconductor components. In addition, with the high integration of semiconductor components, the densification and refinement of semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, and the like constituting the semiconductor components have been advanced, and component-embedded substrates in which chips, chip capacitors, and the like are embedded in substrates have been studied. As a surface protective film or an interlayer insulating layer for a semiconductor component, there are required: a via opening pattern for interlayer connection can be formed; further, the adhesive can be bonded not only to the substrate material and the copper pattern (conductor pattern) but also to the chip component.

As a method for manufacturing a printed wiring board used in the past, a build-up method is exemplified. In the build-up method, first, a surface of an inner layer circuit board (a base material having a first conductor pattern) is chemically or physically surface-treated to form a roughened shape. Next, an insulating resin film is laminated on the roughened inner layer circuit board, and the insulating resin film is cured by heating to form an interlayer insulating layer, and then a via hole is formed by laser processing. Next, the interlayer insulating layer is subjected to roughening treatment and desmearing treatment with alkali permanganic acid or the like, and then electroless copper plating is performed, thereby forming a second conductor pattern and a via hole that can realize interlayer connection (see, for example, patent document 1).

As described above, laser processing is the mainstream as a method for forming a through hole in an interlayer insulating layer, but reduction in the diameter of the through hole by laser irradiation using a laser processing machine is reaching a limit. Further, when the through holes are formed by a laser processing machine, the through holes need to be formed one by one, and when a plurality of through holes are provided due to densification, a large amount of time is required to form the through holes, which causes a problem of poor manufacturing efficiency.

In recent years, with the increase in density of conductor patterns, high resolution has been required for surface protective films, and photosensitive resin compositions capable of patterning by photolithography have come into wide use. Among them, from the viewpoint of work environment protection and global environment protection, an alkali development type photosensitive resin composition capable of being developed by a weakly alkaline aqueous solution such as a sodium carbonate aqueous solution has been mainstream. A method of applying pattern formation by photolithography to via formation has been studied, and for example, patent document 2 proposes a method of using a photosensitive resin composition containing an acid-modified vinyl-containing epoxy resin, a photopolymerizable compound, a photopolymerization initiator, an inorganic filler and a silane compound, the inorganic filler being contained in an amount of 10 to 80 mass%, as a method of forming a large number of through holes at a time by photolithography.

With the miniaturization of the second conductor pattern and the reduction in the diameter of the via hole, it is necessary to reduce the surface roughness on the inner layer circuit board (the base material having the first conductor pattern). On the other hand, in the conventional surface treatment, in order to improve the adhesion with the resin, it is necessary to increase the etching depth (for example, in the example of patent document 3, the copper surface is etched by 1 μm or more), and therefore, when applied to a wiring layer of a printed wiring board, the wire becomes significantly thin, and there is a limit to coping with the miniaturization (narrowing of pitch) of the wiring. Further, if the surface roughness of the conductor is increased due to a large etching depth, there is a problem that a small-diameter opening becomes difficult when a via hole is formed by photolithography using a photosensitive resin composition. On the other hand, if chemical or physical treatment is not performed, there is a problem that the surface roughness of the conductor is reduced and adhesion between the inner layer circuit and the resin (insulating layer) cannot be secured.

As a method for solving the above problems, there are disclosed: an etchant capable of maintaining adhesion between copper and a resin even at a low etching amount (see, for example, patent document 4); a composition for forming a coating film capable of forming a coating film having excellent adhesion to a resin on a metal surface in a short time (for example, see patent document 5); a surface roughening method capable of forming a roughened shape on a copper surface with a low etching amount, which is excellent in adhesion to a resin or the like (see, for example, patent document 6).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 7-304931

Patent document 2: japanese patent laid-open publication No. 2017-116652

Patent document 3: international publication No. 2007/093284

Patent document 4: international publication No. 2014/017115

Patent document 5: japanese patent No. 6387543

Patent document 6: japanese patent No. 6338232

Disclosure of Invention

Problems to be solved by the invention

However, if the etching amount is reduced from, for example, conventional 1 μm to 0.4 μm or less for the purpose of miniaturization of the conductor pattern and reduction in the diameter of the through hole, the following problems occur: the adhesion to the inner layer circuit is reduced, and the adhesion strength to the inner layer circuit cannot be sufficiently obtained both before and after the high temperature and high humidity test.

Accordingly, an object of the present invention is to provide a photosensitive resin composition having excellent adhesion to an inner layer circuit, a photosensitive resin film using the photosensitive resin composition, a printed wiring board, a method for producing the printed wiring board, and a semiconductor package.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, 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 [18 ].

[1] A photosensitive resin composition comprising (A) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent and (B) a photopolymerization initiator,

at least 1 of the components contained in the photosensitive resin composition is a component containing a dicyclopentadiene skeleton.

[2] The photosensitive resin composition according to the above [1], wherein the component containing a dicyclopentadiene skeleton contains a structure represented by the following general formula (X-1),

[ solution 1]

(in the formula, R^X1And R^X2Each independently is a divalent radical having 1 or more groups selected from the group consisting of alkylene, arylene, and oxy. It is a binding site with other structures. )

[3] The photosensitive resin composition according to the above [1] or [2], wherein the total mass of the dicyclopentadiene skeleton contained in the photosensitive resin composition is 5% by mass or more relative to the total solid content of the components contained in the photosensitive resin composition.

[4] The photosensitive resin composition according to any one of the above [1] to [3], wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent is an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by reacting (c) a saturated or unsaturated group-containing polybasic acid anhydride with a resin (A') obtained by reacting (a) an epoxy resin with (b) an ethylenically unsaturated group-containing organic acid.

[5] The photosensitive resin composition according to any one of the above [1] to [4], wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent group contains a dicyclopentadiene skeleton.

[6] The photosensitive resin composition according to the above [4], wherein the photopolymerizable compound (A) having an ethylenically unsaturated group and an acidic substituent comprises:

(A1) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using an epoxy resin having a dicyclopentadiene skeleton as the epoxy resin (a); and

(A2) and (b) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using 1 or more selected from the group consisting of a novolak epoxy resin, a bisphenol epoxy resin and a triphenolmethane epoxy resin as the epoxy resin (a).

[7] The photosensitive resin composition according to any one of the above [1] to [6], further comprising (C) a photopolymerizable compound having no acidic substituent.

[8] The photosensitive resin composition according to the above [7], wherein the photopolymerizable compound (C) having no acidic substituent is a polyfunctional monomer having 3 or more ethylenically unsaturated groups.

[9] The photosensitive resin composition according to the above [7] or [8], wherein the photopolymerizable compound (C) having no acidic substituent comprises a dicyclopentadiene skeleton.

[10] The photosensitive resin composition according to any one of the above [1] to [9], further comprising (D) a thermosetting resin.

[11] The photosensitive resin composition according to any one of the above [1] to [10], further comprising (E) a pigment.

[12] The photosensitive resin composition according to any one of the above [1] to [11], further comprising (F) an inorganic filler.

[13] A photosensitive resin composition for forming a through-hole, comprising the photosensitive resin composition according to any one of the above [1] to [12 ].

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

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

[16] A printed wiring board comprising a surface protective film or an interlayer insulating layer, the surface protective film and the interlayer insulating layer being formed using the photosensitive resin composition according to any one of the above [1] to [12] or the photosensitive resin film according to the above [15 ].

[17] A semiconductor package comprising a semiconductor element mounted on the printed wiring board as recited in the above [16 ].

[18] A method for manufacturing a printed wiring board, comprising the steps of: a step of providing a photosensitive layer on a substrate using the photosensitive resin composition according to any one of the above [1] to [12] or the photosensitive resin film according to [15 ]; a step of forming a resin pattern using the photosensitive layer; and forming at least one of a surface protective film and an interlayer insulating layer by curing the resin pattern.

Effects of the invention

According to the present invention, a photosensitive resin composition having excellent adhesion to an inner layer circuit, a photosensitive resin film using the photosensitive resin composition, a printed wiring board, a method for producing the printed wiring board, and a semiconductor package can be provided.

Drawings

Fig. 1 is a schematic view showing one embodiment of a process for producing a multilayer printed wiring board using a cured product of the photosensitive resin composition of the present embodiment as at least one of a surface protective film and an interlayer insulating layer.

Detailed Description

In the numerical ranges described in the present specification, the upper limit or the lower limit of the numerical range may be replaced with the values shown in the examples. In the present specification, the content of each component in the photosensitive resin composition refers to the total content of a plurality of substances present in the photosensitive resin composition, unless otherwise specified, when a plurality of substances corresponding to each component are present.

In addition, the present invention includes a mode in which items described in the present specification are arbitrarily combined.

In the present specification, the term "resin component" refers to the total amount of components excluding inorganic fillers and diluents which may be contained as required, which will be described later.

In the present specification, the "solid component" means a nonvolatile component excluding volatile substances such as water and a solvent contained in the photosensitive resin composition, and means a component that does not volatilize and remains when the resin composition is dried, and further includes a component that is liquid, syrup-like, or wax-like at room temperature around 25 ℃.

In the present specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar words also mean the same.

[ photosensitive resin composition ]

The photosensitive resin composition of the present embodiment is a photosensitive resin composition containing (a) a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent, and (B) a photopolymerization initiator;

at least 1 of the components contained in the photosensitive resin composition is a component containing a dicyclopentadiene skeleton.

In the present specification, the above components may be simply referred to as component (a) and component (B), respectively, and the same abbreviation may be used for other components.

The photosensitive resin composition of the present embodiment is suitable for forming a through hole by photolithography [ hereinafter, may be referred to as "formation of a through hole". Accordingly, the present invention also provides a photosensitive resin composition for forming a through-hole, which is composed of the photosensitive resin composition of the present embodiment. Further, the photosensitive resin composition of the present embodiment is excellent in resolution, adhesion to an inner layer circuit, and electrical insulation reliability, and is useful as an interlayer insulating layer of a multilayer printed wiring board, and therefore the present invention also provides a photosensitive resin composition for an interlayer insulating layer, which is composed of the photosensitive resin composition of the present embodiment. In the present specification, the term "photosensitive resin composition" also includes a photosensitive resin composition for forming a through-hole 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 the photosensitive resin composition of the present embodiment can contain will be described in detail.

< ingredient containing dicyclopentadiene skeleton >

In the photosensitive resin composition of the present embodiment, at least 1 of the components contained in the photosensitive resin composition is a component containing a dicyclopentadiene skeleton.

The photosensitive resin composition of the present embodiment contains a component containing a dicyclopentadiene skeleton, and thus has excellent adhesion to an inner layer circuit.

In the following description, a component containing a dicyclopentadiene skeleton among components contained in the photosensitive resin composition of the present embodiment may be referred to as "(X) a dicyclopentadiene skeleton-containing compound" or "(X) a component".

The dicyclopentadiene skeleton in the present embodiment refers to a structure represented by the following formula (X-2).

[ solution 2]

(X) the dicyclopentadiene skeleton-containing compound preferably contains a structure represented by the following general formula (X-1).

[ solution 3]

(in the formula, R^X1And R^X2Each independently is a divalent radical having 1 or more groups selected from the group consisting of alkylene, arylene, and oxy. It is a binding site with other structures. )

As R^X1And R^X2Examples of the alkylene group which may be contained include methylene, 1, 2-dimethylene, 1, 3-trimethylene, 1, 4-tetramethylene and 1, 5-pentamethylene. The alkylene group preferably has 1 to 10 carbon atoms. The number of carbon atoms of the alkylene group does not include the number of carbon atoms of the substituent.

The alkylene group may have a substituent or may not have a substituent. Examples of the substituent which the alkylene group may have include: an aromatic hydrocarbon group; a halogen atom; alkoxy, aryloxy, hydroxyl, carboxyl, amino, glycidyl ether; a group formed by combining them, and the like. The number of carbon atoms of the substituent of the alkylene group is preferably 1 to 20, more preferably 1 to 12.

As R^X1And R^X2Examples of the arylene group that may be contained include a phenylene group and a naphthylene group. The alkylene group preferably has 6 to 12 carbon atoms. The number of carbon atoms of the arylene group does not include the number of carbon atoms of the substituent.

The arylene group may have a substituent or may have no substituent. Examples of the substituent which the arylene group may have include: an aliphatic hydrocarbon group; a halogen atom; alkoxy, aryloxy, hydroxyl, carboxyl, amino, glycidyl ether; a group formed by combining them, and the like. The number of carbon atoms of the substituent of the arylene group is preferably 1 to 20, more preferably 1 to 12.

From the viewpoint of improving the adhesion to the inner layer circuit, the adhesion strength to sputtering, and the electrical characteristics, the total mass of the dicyclopentadiene skeleton (i.e., the structure represented by the above general formula (X-1)) contained in the photosensitive resin composition of the present embodiment is preferably not less than 5% by mass, more preferably not less than 7% by mass, and still more preferably not less than 8% by mass, relative to the total solid content of the components contained in the photosensitive resin composition. The total mass of the dicyclopentadiene skeleton may be 15% by mass or less, or may be 10% by mass or less, based on the total solid content of the components contained in the photosensitive resin composition.

The ratio of the molecular weight of the dicyclopentadiene skeleton in the component (X) can be measured by liquid or solid-state NMR. For example, when the ratio of the molecular weight of the dicyclopentadiene skeleton in the component (X) is determined to be P mass%, "the total mass of the dicyclopentadiene skeleton contained in the photosensitive resin composition" (Q parts by mass) "may be calculated as Q (parts by mass) ═ R (parts by mass) × P (parts by mass)/100, based on the total amount of P mass% and the solid content of the component (X) blended in the photosensitive resin composition (R parts by mass).

The (X) dicyclopentadiene skeleton-containing compound may be contained as the component (a) contained in the photosensitive resin composition of the present embodiment, or may be contained as a component other than the component (a), and is preferably contained as the component (a) from the viewpoint of improving adhesion to an inner layer circuit. That is, the component (A) preferably contains a dicyclopentadiene skeleton.

< (A) A photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent

The photosensitive resin composition of the present embodiment contains, as the component (a), a photopolymerizable compound having an ethylenically unsaturated group and an acidic substituent.

(A) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

(A) The component (A) is a compound having an ethylenically unsaturated group to exhibit photopolymerization.

Examples of the ethylenically unsaturated group contained in the component (a) include: a functional group exhibiting photopolymerization such as a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimidyl group, and a (meth) acryloyl group. Among them, from the viewpoint of reactivity and developability, a (meth) acryloyl group is preferable.

From the viewpoint of alkali developability, the component (a) has an acidic substituent.

Examples of the acidic substituent group contained in the component (a) include a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group. Among them, a carboxyl group is preferable from the viewpoint of resolution.

(A) The acid value of the component (A) is preferably 30 to 150mgKOH/g, more preferably 40 to 120mgKOH/g, and still more preferably 50 to 100 mgKOH/g. When the acid value of the component (a) is not less than the lower limit, the solubility of the photosensitive resin composition in a dilute alkali solution tends to be further improved, and when the acid value is not more than the upper limit, the electrical characteristics of the cured film tend to be further improved.

(A) The acid value of the component (A) can be calculated from the amount of 0.1mol/L aqueous potassium hydroxide solution necessary for neutralizing the resin.

(A) The weight average molecular weight (Mw) of the component (B) is preferably 500 to 30,000, more preferably 1,000 to 25,000, and still more preferably 2,000 to 18,000. When the weight average molecular weight (Mw) of the component (a) is within the above range, the adhesion to the inner layer circuit, heat resistance, and insulation reliability tend to be excellent. Here, in the present specification, the weight average molecular weight is a value measured according to the following method.

< method for measuring weight average molecular weight >

The weight average molecular weight is measured by a GPC measuring apparatus and measurement conditions described below, and a value in terms of a standard curve of standard polystyrene is used as the weight average molecular weight. In addition, 5 sample groups ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corp.) were used as standard polystyrene for preparing the calibration curve.

(GPC measurement device)

GPC apparatus: high-speed GPC apparatus "HCL-8320 GPC", the detector being a differential refractometer or UV, manufactured by Tosoh Corp

A chromatographic column: column TSKgel SuperMultipore HZ-H (Column length: 15cm, Column inner diameter: 4.6mm), manufactured by Tosoh corporation

(measurement conditions)

Solvent: tetrahydrofuran (THF)

Measuring temperature: 40 deg.C

Flow rate: 0.35 ml/min

Sample concentration: 10mg/THF 5ml

Injection amount: 20 μ l

(A) The component (b) is preferably an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by reacting (c) a saturated or unsaturated group-containing polybasic acid anhydride [ hereinafter, sometimes simply referred to as (c) a polybasic acid anhydride ] with (a ') a resin obtained by reacting (a) an epoxy resin with (b) an ethylenically unsaturated group-containing organic acid [ hereinafter, sometimes simply referred to as (a') a component ].

Preferred embodiments of the component (A) obtained from (a) an epoxy resin, (b) an organic acid having an ethylenically unsaturated group, and (c) a polybasic acid anhydride having a saturated group or an unsaturated group will be described below.

[ (a) epoxy resin ]

The epoxy resin (a) is preferably an epoxy resin having 2 or more epoxy groups. The epoxy resin can be classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among them, glycidyl ether type epoxy resins are preferable.

(a) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

(a) The epoxy resin may be classified into various epoxy resins according to the difference of the main skeleton, for example, into: epoxy resins having a dicyclopentadiene skeleton, bisphenol type epoxy resins, novolak type epoxy resins, triphenol methane type epoxy resins, aralkyl type epoxy resins, other epoxy resins, and the like.

Among them, the epoxy resin (a) is preferably an epoxy resin having a dicyclopentadiene skeleton, a novolac type epoxy resin, a bisphenol type epoxy resin, or a triphenolmethane type epoxy resin, from the viewpoint of adhesion to the inner layer circuit.

From the viewpoint of adhesion to the inner layer circuit, the component (a) preferably contains:

(A1) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using (a1) an epoxy resin having a dicyclopentadiene skeleton as (a) an epoxy resin; and

(A2) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using (a2) at least one selected from the group consisting of a novolak epoxy resin, a bisphenol epoxy resin and a triphenolmethane epoxy resin as the epoxy resin (a).

The acid-modified ethylenically unsaturated group-containing epoxy derivative (a1) corresponds to the dicyclopentadiene skeleton-containing compound (X) in the present embodiment.

Hereinafter, preferred embodiments of the epoxy resin (a) will be described in more detail.

((a1) component)

(a1) The component is epoxy resin with dicyclopentadiene skeleton.

The photosensitive resin composition of the present embodiment preferably contains (a1) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using the component (a1) as the component (a) from the viewpoint of enabling alkali development and improving resolution and adhesion to an inner layer circuit.

The component (a1) preferably has a structural unit represented by the following general formula (A-1).

[ solution 4]

(in the formula, Y^A1Is a glycidyl group. )

In the epoxy resin having a structural unit represented by the above general formula (A-1), the number of the structural unit is 1 or more, preferably 1 to 10, and more preferably 3 to 7. When the number of the structural units is within the above range, the resolution and the adhesion to the inner layer circuit tend to be further improved.

Here, the number of structural units of a structural unit represents an integer value in a single molecule, and a rational number as an average value in an aggregate of a plurality of kinds of molecules. Hereinafter, the same applies to the number of constituent units.

The epoxy resin having a structural unit represented by the above general formula (A-1) is preferably represented by the following general formula (A-2).

[ solution 5]

(in the formula, Y^A1As illustrated in the above general formula (A-1). Y is^A2And Y^A3Each independently is a hydrogen atom, an alkyl group or a glycidyl group. n is^A1Is a number greater than or equal to 1)

From the viewpoint of improving resolution and adhesion to an inner layer circuit, Y in the general formula (A-2)^A2And Y^A3Glycidyl groups are preferred.

N in the above general formula (A-2)^A1Is a number of 1 or more, preferably 1 to 10, more preferably 3 to 7. If n is^A1Within the above range, the resolution and the adhesion to the inner layer circuit tend to be further improved.

An epoxy resin represented by the above general formula (A-2) (wherein Y^A1、Y^A2And Y^A3Epoxy resins each containing a glycidyl group) are commercially available, for example, as HP-7200H (trade name, manufactured by DIC corporation) and XD-1000 (trade name, manufactured by Nippon Kagaku K.K.).

Further, as the component (a1), an epoxy resin represented by the following general formula (A-3) is also preferably used.

[ solution 6]

(in the formula, Y^A4And Y^A5Each independently is a hydrogen atom, an alkyl group or a glycidyl group. Wherein, Y^A4And Y^A5At least one of which is a glycidyl group. )

From the viewpoint of improving resolution and adhesion to an inner layer circuit, Y in the general formula (A-3)^A4And Y^A5Glycidyl groups are preferred.

An epoxy resin represented by the above general formula (A-3) (wherein Y^A4And Y^A5Epoxy resins all of which are glycidyl groups) are commercially available, for example, from ADEKA RESIN EP-4088S, EP-4088L (all trade names of the products of ADEKA Co., Ltd.).

((a2) component)

(a2) The component (A) is at least 1 selected from the group consisting of novolac epoxy resin, bisphenol epoxy resin and triphenolmethane epoxy resin.

The photosensitive resin composition of the present embodiment preferably contains (a2) an acid-modified ethylenically unsaturated group-containing epoxy derivative obtained by using the component (a2) as the component (a) from the viewpoint of enabling alkali development and improving resolution and adhesion to an inner layer circuit.

The component (a2) is preferably a novolac-type epoxy resin from the viewpoint of improving resolution and adhesion to the inner layer circuit.

Examples of the novolac-type epoxy resin include: bisphenol novolac epoxy resins such as bisphenol a novolac epoxy resin, bisphenol F novolac epoxy resin, and bisphenol S novolac epoxy resin; phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenol novolac type epoxy resins, naphthol novolac type epoxy resins, and the like.

The novolac-type epoxy resin is preferably a bisphenol novolac-type epoxy resin having a structural unit represented by the following general formula (a-4) from the viewpoint of improving resolution and adhesion to an inner layer circuit.

[ solution 7]

(in the formula, R^A1And R^A2Each independently being a hydrogen atom or a methyl group, Y^A6And Y^A7Each independently is a hydrogen atom, an alkyl group or a glycidyl group. Wherein, Y^A6And Y^A7At least one of which is a glycidyl group. )

From the viewpoint of improving resolution and adhesion to an inner layer circuit, R^A1And R^A2Preferably a hydrogen atom.

From the same viewpoint, Y^A6And Y^A7Glycidyl groups are preferred.

In the epoxy resin having a structural unit represented by the general formula (A-4), the number of the structural unit is not less than 1, preferably 10 to 100, more preferably 15 to 80, and further preferably 15 to 70. When the number of the structural units is within the above range, the resolution and the adhesion to the inner layer circuit tend to be further improved.

The novolac-type epoxy resin is more preferably a bisphenol novolac-type epoxy resin having a structural unit represented by the following general formula (a-5) from the viewpoint of improving resolution and adhesion to an inner layer circuit.

[ solution 8]

(in the formula, R^A3And R^A4Each independently being a hydrogen atom or a methyl group, Y^A8And Y^A9Each independently is a hydrogen atom, an alkyl group or a glycidyl group. Wherein, Y^A8And Y^A9At least one of which is a glycidyl group. )

From the viewpoint of improving resolution and adhesion to an inner layer circuit, R^A3And R^A4Preferably a hydrogen atom.

From the same viewpoint, Y^A8And Y^A9Glycidyl groups are preferred.

In the epoxy resin having a structural unit represented by the general formula (A-5), the number of the structural unit is not less than 1, preferably 10 to 100, more preferably 15 to 80, and further preferably 15 to 70. When the number of the structural units is within the above range, the adhesive strength, heat resistance and electrical insulation properties tend to be further improved.

In the above general formula (A-5), R^A3And R^A4Is a hydrogen atom and Y^A8And Y^A9Epoxy resins as glycidyl groups are commercially available, for example, as EXA-7376 series (trade name, available from DIC corporation), and R^A3And R^A4Is methyl and Y^A8And Y^A9Epoxy resins that are glycidyl groups are commercially available, for example, in EPON SU8 series (product name, manufactured by mitsubishi chemical corporation).

Further, as the novolac-type epoxy resin, a phenol novolac-type epoxy resin having a structural unit represented by the following general formula (a-6) is also preferable.

[ solution 9]

(in the formula, R^A5Is a hydrogen atom or a methyl group, Y^A10Is a glycidyl group. )

The epoxy resin having a structural unit represented by the above general formula (A-6) may contain Y in the above general formula (A-6)^A10Is a structural unit of a hydrogen atom. In this case, from the viewpoint of improving the resolution, Y is^A10Structural unit (U) being a hydrogen atom_H) And Y^A10Structural unit (U) being a glycidyl group_G) Molar ratio of [ (U)_H)/(U_G)]Preferably 0/100-30/70, more preferably 0/100-10/90.

Examples of the epoxy resin having a structural unit represented by the above general formula (a-6) include phenol novolac type epoxy resins, cresol novolac type epoxy resins, and the like. These novolak-type epoxy resins can be obtained by, for example, reacting a phenol novolak resin, a cresol novolak resin, and epichlorohydrin by a known method.

As the phenol novolak-type epoxy resin or cresol novolak-type epoxy resin represented by the above general formula (a-6), for example, there are commercially available: YDCN-701, YDCN-702, YDCN-703, YDCN-704L, YDPN-638, and YDPN-602 (trade name, manufactured by Nissan chemical Co., Ltd.); DEN-431 and DEN-439 (trade names of the "Dow chemical Co., Ltd."); EOCN-120, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (trade name, manufactured by Nippon chemical Co., Ltd.); EPN-1138, EPN-1235, EPN-1299 (trade name, manufactured by BASF Corp.); n-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (trade name, available from DIC corporation) and the like.

Examples of the bisphenol epoxy resin used as the component (a2) include bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -diglycidyloxydiphenylmethane.

As the bisphenol a type epoxy resin or the bisphenol F type epoxy resin, for example, Epikote 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, and 1009 (above, manufactured by mitsubishi chemical corporation, trade name) are commercially available; DER-330, DER-301, and DER-361 (trade name, available from Dow chemical Co., Ltd.); YD-8125, YDF-170, YDF-175S, YDF-2001, YDF-2004, and YDF-8170 (trade name, manufactured by Nissan chemical Co., Ltd.).

As the trisphenolmethane type epoxy resin used as the component (a2), for example, FAE-2500, EPPN-501H, EPPN-502H (manufactured by Nippon Kagaku K.K., trade name) and the like are commercially available.

(a) The epoxy resin other than the above-mentioned (a1) component and (a2) component may be used.

Examples of the epoxy resin other than the (a1) component and the (a2) component include: aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like; stilbene type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, dihydroanthracene type epoxy resin, cyclohexane dimethanol type epoxy resin, trimethylol type epoxy resin, alicyclic type epoxy resin, aliphatic chain epoxy resin, heterocyclic type epoxy resin, spiro ring-containing epoxy resin, rubber modified epoxy resin, hydrogenated bisphenol a type epoxy resin, and the like.

[ (b) organic acids containing ethylenically unsaturated groups ]

(b) The organic acid containing an ethylenically unsaturated group is not particularly limited as long as it is an organic acid containing an ethylenically unsaturated group.

Examples of the ethylenically unsaturated group contained in the component (b) include the same groups as those contained in the component (A). Among them, from the viewpoint of reactivity and resolution, (meth) acryloyl groups are preferable.

(b) The organic acid having an ethylenically unsaturated group is not particularly limited, but is preferably a monocarboxylic acid having an ethylenically unsaturated group.

Examples of the monocarboxylic acid having an ethylenically unsaturated group include: acrylic acid; acrylic acid derivatives such as acrylic acid dimer, methacrylic acid, β -furfurylacrylic acid, β -styrylacrylic acid, cinnamic acid, crotonic acid, and α -cyanocinnamic acid; a half ester compound which is a reaction product of a hydroxyl group-containing acrylate and a dibasic acid anhydride; and half ester compounds which are reaction products of vinyl group-containing monoglycidyl ethers or vinyl group-containing monoglycidyl esters with dibasic acid anhydrides, and the like. Among them, acrylic acid is preferable.

(b) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

The half ester compound can be obtained, for example, by reacting an ethylenically unsaturated group-containing compound selected from the group consisting of a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether and a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride. The reaction is preferably carried out by reacting the compound having an ethylenically unsaturated group with the dibasic acid anhydride in equimolar amounts.

Examples of the hydroxyl group-containing acrylate used for the synthesis of the half ester compound include: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

Examples of the vinyl group-containing monoglycidyl ether include glycidyl (meth) acrylate.

The dibasic acid anhydride used for the synthesis of the half 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, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like.

In the reaction of the component (a) and the component (b), the amount of the component (b) used is preferably 0.6 to 1.05 equivalents, more preferably 0.7 to 1.02 equivalents, and still more preferably 0.8 to 1.0 equivalent, relative to 1 equivalent of the epoxy group of the component (a). By reacting the component (a) and the component (b) at the above ratio, the photopolymerization of the component (a) tends to be improved, and the resolution of the obtained photosensitive resin composition tends to be improved.

(a) The component (b) and the component (b) are preferably dissolved in an organic solvent to react.

Examples of the organic solvent include: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl cellosolve acetate, carbitol acetate, and the like; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like. The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

In the reaction of the component (a) and the component (b), a catalyst for promoting the reaction is preferably used. Examples of the catalyst include: amine catalysts such as triethylamine and benzylmethylamine; quaternary ammonium salt catalysts such as methyltriethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide and the like; phosphine catalysts such as triphenylphosphine. Among them, a phosphine-based catalyst is preferable, and triphenylphosphine is more preferable. The catalyst may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the catalyst is used, the amount of the catalyst used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the total of the components (a) and (b), from the viewpoint of allowing the reaction to proceed homogeneously while obtaining sufficient reactivity.

In the reaction of the component (a) and the component (b), a polymerization inhibitor is preferably used for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like. The polymerization inhibitor may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When a polymerization inhibitor is used, the amount of the polymerization inhibitor is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 part by mass, and still more preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the total of the components (a) and (b), from the viewpoint of improving the storage stability of the composition.

The reaction temperature of the component (a) and the component (b) is preferably 60 to 150 ℃, more preferably 80 to 120 ℃, and even more preferably 90 to 110 ℃ from the viewpoint of allowing the reaction to proceed homogeneously while obtaining sufficient reactivity.

The component (a') obtained by reacting the component (a) and the component (b) in this way has a hydroxyl group formed by a ring-opening addition reaction of an epoxy group of the component (a) and a carboxyl group of the component (b). Then, by further reacting the component (c) with the component (a '), the hydroxyl group of the component (a') (including the hydroxyl group originally present in the component (a)) is half-esterified with the acid anhydride group of the component (c), whereby an acid-modified ethylenically unsaturated group-containing epoxy derivative can be obtained.

[ (c) polybasic acid anhydride ]

The component (c) may contain a saturated group or an unsaturated group. Examples of the component (c) include: succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like. Among them, tetrahydrophthalic anhydride is preferable from the viewpoint of resolution. (c) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

In the reaction of the component (a ') and the component (c), the acid value of the obtained component (a) can be adjusted by, for example, reacting 0.1 to 1.0 equivalent of the component (c) with respect to 1 equivalent of the hydroxyl group in the component (a').

From the viewpoint of productivity, the reaction temperature of the component (A') and the component (c) is preferably 50 to 150 ℃, more preferably 60 to 120 ℃, and still more preferably 70 to 110 ℃.

In addition to the above, the component (a) may be partially combined with a styrene-maleic acid resin such as a hydroxyethyl (meth) acrylate-modified styrene-maleic anhydride copolymer.

(content of component (A))

(A) The content of the component is not particularly limited, but is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 15 to 40% by mass based on the total solid content of the photosensitive resin composition, from the viewpoint of further improving heat resistance, electrical characteristics, and chemical resistance.

< (B) photopolymerization initiator

The photosensitive resin composition of the present embodiment further contains a photopolymerization initiator as the component (B).

The photosensitive resin composition of the present embodiment contains (B) a photopolymerization initiator, and thus the sensitivity tends to be improved, and the exposed portion tends not to be easily eluted during development.

The photopolymerization initiator (B) is not particularly limited as long as it is capable of polymerizing the component (a), and can be appropriately selected from generally used photopolymerization initiators.

Examples of the photopolymerization initiator (B) include: benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and the like; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, and N, N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2, 4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenones such as benzophenone, methylbenzophenone, 4 '-dichlorobenzophenone, 4' -bis (diethylamino) benzophenone, Michler's ketone, and 4-benzoyl-4' -methylbenzophenone sulfide; acridines such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane; acylphosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; oxime esters such as 1, 2-octanedione-1- [4- (phenylthio) phenyl ] -2- (O-benzoyloxime), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), and 1-phenyl-1, 2-propanedione-2- [ O- (ethoxycarbonyl) oxime ].

Among them, acetophenones are preferable from the viewpoint of being not volatile and not easily generating as a boil-off gas.

(B) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds. When 2 or more kinds are used in combination, acetophenone, thioxanthone and oxime ester are preferably used in combination.

The photosensitive resin composition of the present embodiment may use, together with component (B), a photopolymerization initiator such as a tertiary amine, e.g., ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, triethylamine, or triethanolamine.

(content of component (B))

(B) The content of the component is not particularly limited, but is preferably 0.2 to 15% by mass, more preferably 0.4 to 5% by mass, and still more preferably 0.6 to 1% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (B) is greater than or equal to the lower limit, the possibility that the exposed portion may be eluted during development tends to be reduced in the interlayer insulating layer formed using the photosensitive resin composition, and if the content is less than or equal to the upper limit, the heat resistance tends to be further improved.

[ C ] photopolymerizable Compound

The photosensitive resin composition of the present embodiment preferably further contains a photopolymerizable compound having no acidic substituent as the component (C).

(C) The component (b) is not particularly limited as long as it is a compound capable of photopolymerization, and examples thereof include: a monomer having 1 ethylenically unsaturated group, a monomer having 2 ethylenically unsaturated groups, a monomer having 3 or more ethylenically unsaturated groups, and the like. Examples of the ethylenically unsaturated group contained in the component (C) include the same groups as those of the ethylenically unsaturated group contained in the component (A), and preferred groups are also the same.

(C) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

Examples of the component (C) include: hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; mono-or di (meth) acrylates of glycols such as ethylene glycol, methoxy tetraethylene glycol, and polyethylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; polyhydric (meth) acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris (hydroxyethyl) isocyanurate, or ethylene oxide or propylene oxide adducts thereof; (meth) acrylic acid esters of ethylene oxide or propylene oxide adducts of phenols such as phenoxyethyl (meth) acrylate and polyethoxy di (meth) acrylate of bisphenol A; (meth) acrylic acid esters of glycidyl ethers such as glycerol diglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; melamine (meth) acrylates, and the like.

The component (C) is preferably a polyfunctional monomer having 3 or more ethylenically unsaturated groups from the viewpoint of increasing the crosslinking density by photocuring and improving the heat resistance and electrical reliability. Such a compound includes the above-mentioned polyvalent (meth) acrylates, and dipentaerythritol tri (meth) acrylate is preferable from the viewpoint of improving sensitivity.

From the viewpoint of adhesion to the inner layer circuit, the component (C) preferably contains an alicyclic skeleton, and more preferably contains a dicyclopentadiene skeleton.

From the same viewpoint, the component (C) is preferably a di (meth) acrylate having an alicyclic skeleton, and more preferably a difunctional (meth) acrylate having a dicyclopentadiene skeleton. Examples of the difunctional (meth) acrylate having a dicyclopentadiene skeleton include tricyclodecane dimethanol diacrylate and the like.

The difunctional (meth) acrylate having a dicyclopentadiene skeleton is commercially available, for example, from FA-513M (manufactured by Hitachi chemical Co., Ltd., trade name); DCP and A-DCP (trade name, manufactured by Ningzhou chemical industries, Ltd.).

When the photosensitive resin composition of the present embodiment contains a bifunctional (meth) acrylate having a dicyclopentadiene skeleton as the component (C), the bifunctional (meth) acrylate having a dicyclopentadiene skeleton corresponds to (X) the compound containing a dicyclopentadiene skeleton.

(C) The molecular weight of the photopolymerizable compound is preferably less than 1,000, more preferably 150 to 800, still more preferably 200 to 700, and particularly preferably 250 to 600.

When the photosensitive resin composition of the present embodiment contains (C) the photopolymerizable compound, the content of the (C) photopolymerizable compound is not particularly limited, but is preferably 2 to 50% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (C) is greater than or equal to the lower limit, the sensitivity tends to be improved and the exposed portion tends not to be easily eluted during development, and if the content is less than or equal to the upper limit, the heat resistance tends to be further improved.

(D) thermosetting resin

The photosensitive resin composition of the present embodiment preferably further contains a thermosetting resin as the component (D). Wherein the component (D) does not contain substances corresponding to the components (A) and (B).

The photosensitive resin composition of the present embodiment contains the thermosetting resin (D), and thus not only resolution and adhesion to an inner layer circuit are improved, but also heat resistance tends to be further improved.

(D) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

Examples of the thermosetting resin (D) include: epoxy resins, phenol resins, unsaturated imide resins, cyanate ester resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, and the like. In addition, the resin composition is not particularly limited thereto, and a known thermosetting resin can be used. Among them, epoxy resins are preferable.

The epoxy resin is preferably an epoxy resin having 2 or more epoxy groups. The epoxy resin can be classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among them, glycidyl ether type epoxy resins are preferable.

In addition, the epoxy resin can be classified into various types of epoxy resins according to the difference in the main skeleton, and among the above various types of epoxy resins, the following can be further classified. Specifically, it can be classified into: bisphenol epoxy resins such as bisphenol a epoxy resin, bisphenol F epoxy resin, and bisphenol S epoxy resin; bisphenol novolac epoxy resins such as bisphenol a novolac epoxy resin and bisphenol F novolac epoxy resin; novolac-type epoxy resins other than the bisphenol-type novolac epoxy resin, such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, and biphenol novolac-type epoxy resins; a phenol aralkyl type epoxy resin; a stilbene type epoxy resin; naphthalene skeleton-containing epoxy resins such as naphthalene-type epoxy resins, naphthol novolac-type epoxy resins, naphthol phenol-type epoxy resins, naphthol aralkyl-type epoxy resins, and naphthylene ether-type epoxy resins; biphenyl type epoxy resin; biphenyl aralkyl type epoxy resins; a xylylene type epoxy resin; a dihydroanthracene type epoxy resin; dicyclopentadiene type epoxy resins; an alicyclic epoxy resin; a heterocyclic epoxy resin; epoxy resins containing spiro rings; cyclohexane dimethanol type epoxy resins; a trimethylol type epoxy resin; an aliphatic chain epoxy resin; rubber-modified epoxy resins, and the like.

Among them, from the viewpoint of improving heat resistance, bisphenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins are preferable, bisphenol a type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins are more preferable, bisphenol F type epoxy resins and biphenyl type epoxy resins are even more preferable, and biphenyl type epoxy resins are particularly preferable.

Commercially available products may be used as these, and examples thereof include: bisphenol a type epoxy resin (product "jER 828 EL", "YL 980" by mitsubishi chemical corporation), bisphenol F type epoxy resin (product "jER 806H" by mitsubishi chemical corporation and "YL 983U", naphthalene type epoxy resin (product "HP 4032D" by DIC corporation and "HP 4710"), naphthalene skeleton-containing type polyfunctional epoxy resin (product "NC 7000" by mitsubishi chemical corporation), naphthol type epoxy resin (product "ESN-475V" by mitsubishi chemical corporation), epoxy resin having a biphenyl structure (product "NC 3000H" by mitsubishi chemical corporation and "NC 3500", product "YX 4000 HK" by mitsubishi chemical corporation and "YL 6121"), anthracene type epoxy resin (product "YX 8800" by mitsubishi chemical corporation) and glycerol type epoxy resin (product "ZX 2" by mitsubindium chemical corporation and the like) (product "EXA 677311-4" by mitsubishi chemical corporation).

In addition, the component (D) is also preferably a dicyclopentadiene type epoxy resin from the viewpoint of adhesion to the inner layer circuit.

The preferable embodiment of the dicyclopentadiene type epoxy resin is the same as that described for the epoxy resin (a1), and the commercially available products include those similar to those listed as the component (a 1).

When the photosensitive resin composition of the present embodiment contains a dicyclopentadiene type epoxy resin as the component (D), the dicyclopentadiene type epoxy resin corresponds to (X) the dicyclopentadiene skeleton-containing compound.

As the epoxy resin, in addition to the above, epoxy-modified polybutadiene [ hereinafter, also referred to as epoxidized polybutadiene in some cases may be used. ]. In particular, from the viewpoint of handling properties in the production of a 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 as the component (D), and from this viewpoint, it is preferable to use an epoxy resin (an aromatic epoxy resin that is solid at room temperature) and an epoxy-modified polybutadiene (an epoxy resin that is liquid at room temperature) that have been exemplified as being preferable in combination. In this case, the content ratio (aromatic epoxy resin which is solid at room temperature/epoxy resin which is liquid at room temperature) of the two components used together is preferably 95/5 to 60/40, more preferably 95/5 to 70/30, and still more preferably 90/10 to 75/25 in terms of mass ratio.

The epoxy-modified polybutadiene preferably has a hydroxyl group at a molecular terminal, more preferably has a hydroxyl group at both molecular terminals, and still more preferably has a hydroxyl group only at both molecular terminals. The number of hydroxyl groups 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 still more preferably 2.

The epoxy-modified polybutadiene is preferably an epoxy-modified polybutadiene represented by the following general formula (D-1) from the viewpoint of adhesion to an inner layer circuit, heat resistance, thermal expansion coefficient and flexibility.

[ solution 10]

(wherein a, b and c represent the ratio of structural units in parentheses, a is 0.05 to 0.40, b is 0.02 to 0.30, c is 0.30 to 0.80, and a + b + c is 1.00 and (a + c) > b.y represents the number of structural units in parentheses, and is an integer of 10 to 250.)

In the above general formula (D-1), the connection order of the respective structural units in parentheses is different. 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 located at different positions, and if represented by (a), (b), (c), respectively, there may be various connection orders as follows: - [ (a) - (b) - (c) ] - [ (a) - (b) - (c) - ] -, - [ (a) - (c) - (b) ] - [ (a) - (c) - (b) - ] -, - [ (b) - (a) - (c) ] - [ (b) - (c) - ] -, - (b) - (a) - (c) - ] -, - [ (a) - (b) - (c) ] - [ (c) - (b) - (a) - ] -, - [ (a) - (b) - (a) ] - [ (c) - (b) - (c) - ] -, - [ (c) - (b) - (c) ] - [ (b) - (a) - ] -, etc.

From the viewpoint of adhesion to the inner layer circuit, heat resistance, thermal expansion coefficient and flexibility, a is preferably 0.10 to 0.30, b is preferably 0.10 to 0.30, and c is preferably 0.40 to 0.80. From the same viewpoint, y is preferably an integer of 30 to 180.

In the general formula (D-1), examples of commercially available epoxidized polybutadiene in which a is 0.20, b is 0.20, c is 0.60, and y is an integer of 10 to 250 include "EPOLEAD (registered trademark) PB 3600" (manufactured by cellosolve corporation).

(content of component (D))

When the photosensitive resin composition of the present embodiment contains the component (D), the content of the component (D) is not particularly limited, but is preferably 5 to 70% by mass, more preferably 5 to 40% by mass, further preferably 7 to 30% by mass, and particularly preferably 10 to 20% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (D) is not less than the lower limit, the photosensitive resin composition can be sufficiently crosslinked, and the adhesiveness to the inner layer circuit and the electrical insulation reliability tend to be improved. On the other hand, if the content of the component (D) is less than or equal to the upper limit value, the resolution tends to be good.

< (E) pigment

The photosensitive resin composition of the present embodiment may further contain a pigment as the component (E).

The photosensitive resin composition of the present embodiment can adjust the photosensitivity by containing (E) a pigment.

The pigment (E) may be used by appropriately selecting a colorant emitting a desired color, and examples thereof include: phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like.

(E) The pigment may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(content of (E) pigment)

When the photosensitive resin composition of the present embodiment contains the pigment (E), the content of the pigment (E) is not particularly limited, and is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and further preferably 0.05 to 2% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of sensitivity adjustment and the like.

(F) inorganic filler

The photosensitive resin composition of the present embodiment preferably further contains an inorganic filler as the component (F). The photosensitive resin composition of the present embodiment can further reduce thermal expansion and reduce the possibility of occurrence of warpage by containing (F) an inorganic filler.

Examples of the inorganic filler (F) include: silicon dioxide (SiO)₂) Alumina (Al)₂O₃) Titanium oxide (TiO)₂) Tantalum oxide (Ta)₂O₅) Zirconium oxide (ZrO)₂) Silicon nitride (Si)₃N₄) Barium titanate (BaO. TiO)₂) Barium carbonate (BaCO)₃) Magnesium carbonate (MgCO)₃) Aluminum hydroxide (Al (OH)₃) Magnesium hydroxide (Mg (OH)₂) Lead titanate (PbO. TiO)₂) Lead zirconate titanate(PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga)₂O₃) Spinel (MgO. Al)₂O₃) Mullite (3 Al)₂O₃·2SiO₂) Cordierite (2 MgO.2Al)₂O₃/5SiO₂) Talc (3 MgO.4SiO)₂·H₂O), aluminum Titanate (TiO)₂·Al₂O₃) Yttria-containing zirconia (Y)₂O₃·ZrO₂) Barium silicate (BaO 8 SiO)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, and the like. (F) The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

From the viewpoint of resolution, the average particle diameter of the inorganic filler (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, still more preferably 0.3 to 2 μm, and particularly preferably 0.5 to 1.5. mu.m.

Here, the average particle diameter of the (F) inorganic filler is a volume average particle diameter of the inorganic filler in a state of being dispersed in the photosensitive resin composition, and is a value measured in the following manner. First, after the photosensitive resin composition was diluted (or dissolved) to 1,000 times with methyl ethyl ketone, the particles dispersed in the solvent were measured for a refractive index of 1.38 using a submicron particle analyzer (product name: N5, manufactured by beckmann coulter corporation) in accordance with international standard ISO13321, and the particle diameter at a cumulative value of 50% (volume basis) in the particle size distribution was defined as an average particle diameter (volume average particle diameter). The inorganic filler (F) contained in the photosensitive resin film and the interlayer insulating film provided on the carrier film may be diluted (or dissolved) with a solvent to 1,000 times (volume ratio) as described above and then measured by the above-mentioned submicron particle analyzer.

From the viewpoint of improving dispersibility in the photosensitive resin composition by the aggregation preventing effect, it is preferable that the inorganic filler (F) is surface-treated with alumina or an organic silane compound in advance. Further, the surface roughness of the cured product subjected to the roughening treatment or desmear treatment can be further reduced by the surface treatment, and further fine wiring can be formed on the surface of the cured product.

(F) content of inorganic Filler)

When the photosensitive resin composition of the present embodiment contains (F) an inorganic filler, the content of the (F) inorganic filler is not particularly limited, but is preferably 10 to 80% by mass, more preferably 12 to 70% by mass, even more preferably 15 to 65% by mass, and particularly preferably 18 to 60% by mass, based on the total solid content of the photosensitive resin composition. If the content of (F) the inorganic filler is within the above range, mechanical strength, heat resistance, resolution, and the like can be improved.

< (G) elastomer

The photosensitive resin composition of the present embodiment preferably further contains an elastomer as the component (G).

The photosensitive resin composition of the present embodiment tends to have more excellent resolution, adhesion to an inner layer circuit, and electrical insulation reliability by containing the (G) elastomer. Further, the component (D) also has the following effects: the deterioration of flexibility and adhesion to the inner layer circuit due to internal deformation (internal stress) of the cured product caused by curing shrinkage of the component (A) is suppressed.

As the component (G), an elastomer which is liquid at 25 ℃ is preferable.

(G) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

Examples of the elastomer (G) include: styrene elastomers, olefin elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers, and the like. These elastomers are composed of a hard segment component and a soft segment component, and generally speaking, the former contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.

Among them, polyester elastomers are preferable.

Examples of the polyester elastomer include polyester elastomers obtained by polycondensation of a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof. The polyester elastomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Examples of the dicarboxylic acid include: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; an aromatic dicarboxylic acid in which a hydrogen atom of an aromatic ring of the aromatic dicarboxylic acid is substituted with a methyl group, an ethyl group, a phenyl group, or the like; aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid, dodecanedioic acid, and the like; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the dicarboxylic acid, a dimer acid derived from natural products is also preferably used from the viewpoint of adhesion to a substrate. The dicarboxylic acid may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Examples of the derivative of the dicarboxylic acid include anhydrides of the dicarboxylic acids.

Examples of the diol compound include: aliphatic diols such as ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 10-decanediol; alicyclic diols such as 1, 4-cyclohexanediol; and aromatic diols such as bisphenol a, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcinol. The diol compounds may be used alone in 1 kind, or in combination of 2 or more kinds.

Further, as the polyester elastomer, a multiblock copolymer having an aromatic polyester (e.g., polybutylene terephthalate) portion as a hard segment component and an aliphatic polyester (e.g., polytetramethylene glycol) portion as a soft segment component may be used, and the multiblock copolymer is preferably used. The multiblock copolymer is commercially available in various grades depending on the kind, ratio and molecular weight of the hard block and the soft block, and specifically includes: "Hytrel (registered trademark)" (manufactured by tokyo corporation), "PELPRENE (registered trademark)" (manufactured by tokyo corporation), "Espel (registered trademark)" (manufactured by hitachi chemical corporation), and the like.

The number average molecular weight of the polyester elastomer is preferably 900 to 30,000, more preferably 1,000 to 25,000, and further preferably 5,000 to 20,000.

As the polyester elastomer, commercially available products can be used, and as commercially available products other than those mentioned above, for example, Teslac 2505-63 (manufactured by Hitachi chemical Co., Ltd. "Teslac" is a registered trademark) and the like are commercially available.

(content of component (G))

When the photosensitive resin composition of the present embodiment contains the component (G), the content of the component (G) is not particularly limited, but is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 3 to 10% by mass, based on the total solid content of the photosensitive resin composition. When the content of the (G) elastomer is within the above range, the thermal shock resistance and the adhesion to the inner layer circuit tend to be further improved while maintaining good developability. In addition, when used for a film substrate, the warping property of the film substrate can be reduced.

(H) epoxy resin curing agent

The photosensitive resin composition of the present embodiment may further contain an epoxy resin curing agent as the component (H).

The photosensitive resin composition of the present embodiment contains (H) the epoxy resin curing agent, and thus various properties such as heat resistance, adhesive strength, and chemical resistance tend to be further improved.

Examples of the epoxy resin curing agent (H) include: imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylylenediamine, diaminodiphenylsulfone, dicyandiamide, urea derivatives, melamine, polyhydrazide, and the like; organic acid salts and/or epoxy adducts thereof; an amine complex of boron trifluoride; triazine derivatives such as ethyldiamino-S-triazine, 2, 4-diamino-S-triazine, and 2, 4-diamino-6-xylylene-S-triazine.

(H) The epoxy resin curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(content of component (H))

When the photosensitive resin composition of the present embodiment contains the component (H), the content of the component (H) is not particularly limited, and is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass, and further preferably 0.1 to 3% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of further suppressing the influence on the photosensitive characteristics. When the content of the elastomer (H) is within the above range, the thermal shock resistance and the adhesion to the inner layer circuit can be further improved while maintaining good developability. In addition, when used for a film substrate, the warping property of the film substrate can be reduced.

As described above, the photosensitive resin composition of the present embodiment preferably contains 1 or more selected from the group consisting of the component (C), the component (D), the component (E), the component (F), the component (G) and the component (H), and the component (C), the component (D), the component (E), the component (F), the component (G) or the component (H) may not be contained depending on the desired performance.

< Diluent >

A diluent may be used as necessary in the photosensitive resin composition of the present embodiment. 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; glycol ethers such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, carbitol acetate, and the like; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, and the like. The diluent may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

(content of Diluent)

The content of the diluent may be appropriately selected so that the concentration of the total solid content of the photosensitive resin composition is preferably 45 to 90 mass%, more preferably 50 to 80 mass%, and still more preferably 55 to 70 mass%. When the content of the diluent is within the above range, the applicability of the photosensitive resin composition is improved, and a higher definition pattern can be formed.

The photosensitive resin composition of the present embodiment may not contain a diluent.

< 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; tackifiers such as bentonite and montmorillonite; defoaming agents such as silicone defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; and various known and conventional additives such as silane coupling agents. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, phosphate compounds of antimony compounds and phosphorus compounds, aromatic condensed phosphate esters, and halogen-containing condensed phosphate esters may be contained. The photosensitive resin composition of the present embodiment may contain no such additives.

The photosensitive resin composition of the present embodiment can be produced by kneading and mixing the respective components by a roll mill, a bead mill, or the like.

Here, the photosensitive resin composition of the present embodiment may be used in a liquid form or a film form.

When the photosensitive resin composition is used in a liquid form, the method of applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include various application methods such as a printing method, a spin coating method, a spray coating method, a jet dispensing method, an ink jet method, and a dip coating method. Among them, from the viewpoint of easier formation of the photosensitive layer, it is preferable to appropriately select from a printing method and a spin coating method.

When used in the form of a film, the film can be used in the form of, for example, a photosensitive resin film described later. The photosensitive resin film can be laminated on a substrate using a laminator or the like to form a photosensitive layer. When used in the form of a film, the multilayer printed wiring board is preferably used because the production 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 composed of the photosensitive resin composition of the present embodiment. The photosensitive resin film of the present embodiment may be formed by disposing the photosensitive resin film on a carrier film.

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 1 to 50 μm, and still more preferably 5 to 40 μm, from the viewpoint of thinning of the printed wiring board.

The photosensitive resin film of the present embodiment can be produced, for example, by coating the photosensitive resin composition of the present embodiment on a carrier film and drying the coating. As the coating apparatus, for example, a known coating apparatus such as a missing-corner wheel coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used.

Examples of the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyolefins such as polypropylene and polyethylene. The thickness of the carrier film is, for example, 5 to 100 μm, preferably 5 to 60 μm, and more preferably 15 to 45 μm.

The photosensitive resin film of the present embodiment may be provided with a protective film on the surface opposite to the surface contacting the carrier film. As the protective film, for example, a polymer film of polyethylene, polypropylene, or the like can be used. The carrier film may be the same polymer film as the carrier film, or may be a different polymer film.

The coating film formed by applying the photosensitive resin composition can be dried by, for example, a dryer using hot air, far infrared rays, or near infrared rays. The drying temperature is preferably 60 to 150 ℃, more preferably 70 to 120 ℃, and further preferably 80 to 100 ℃. The drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and still 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, and still more preferably 1% by mass or less, from the viewpoint of avoiding the diffusion of the diluent in the production process of the printed wiring board.

The photosensitive resin film of the present embodiment is excellent in resolution, adhesion to an inner layer circuit, and electrical insulation reliability, and therefore is suitable as an interlayer insulating layer of a multilayer printed wiring board. That is, the present invention also provides a photosensitive resin film for an interlayer insulating layer. The photosensitive resin film for an interlayer insulating layer may also be referred to as an interlayer insulating photosensitive film.

[ printed Wiring Board and method for producing the same ]

The printed wiring board of the present embodiment is a printed wiring board including a surface protective film or an interlayer insulating layer formed using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment.

The printed wiring board of the present embodiment can be manufactured by a method including, in order: a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment; a step of forming a resin pattern using the photosensitive layer; and forming at least one of a surface protective film and an interlayer insulating layer by curing the resin pattern.

Hereinafter, an example of the method for manufacturing a printed wiring board according to the present embodiment will be described with reference to fig. 1 as appropriate.

First, a photosensitive layer is formed on a metal-clad laminate such as a copper-clad laminate by a method of coating a photosensitive resin composition or a method of laminating a photosensitive resin film.

Examples of the method for applying the photosensitive resin composition include screen printing, spraying, roll coating, curtain coating, and electrostatic coating. The thickness at the time of coating is preferably 1 to 100 μm, more preferably 1 to 50 μm, and further preferably 5 to 40 μm in terms of the film thickness after drying. The drying temperature after coating is, for example, 60 to 110 ℃. The photosensitive resin film may be laminated by heat lamination using a known laminator.

Then, a negative film is brought into direct contact with the photosensitive layer (or into non-contact with a transparent film such as a carrier film) at a thickness of, for example, 10 to 2,000mJ/cm²Preferably 100 to 1,500mJ/cm²More preferably 300 to 1,000mJ/cm²The exposure amount of the light source is used to irradiate the active light,then, the unexposed portion is dissolved and removed (developed) using a dilute aqueous alkali solution to form a pattern. Examples of the active light that can be used include electron beams, ultraviolet rays, and X-rays. Ultraviolet rays are preferred. As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, or the like can be used.

Subsequently, the exposed portion of the photosensitive layer is sufficiently cured by at least one of post-exposure (ultraviolet exposure) and post-heating, thereby forming at least one of a surface protective film and an interlayer insulating layer.

The exposure amount of the post-exposure is, for example, 100 to 5,000mJ/cm²Preferably 500 to 2,000mJ/cm²More preferably 700 to 1,500mJ/cm²。

The post-heating temperature is, for example, 100 to 200 ℃, preferably 120 to 180 ℃, and more preferably 135 to 165 ℃.

The heating time of the post-heating is, for example, 5 minutes to 12 hours, preferably 10 minutes to 6 hours, and more preferably 30 minutes to 2 hours.

Then, a conductor pattern is formed by etching, thereby producing a printed wiring board.

Further, a multilayer printed wiring board can also be produced using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment.

Fig. 1 is a schematic view showing one embodiment of a process for producing a multilayer printed wiring board using a cured product of the photosensitive resin composition of the present embodiment as at least one of a surface protective film and an interlayer insulating layer.

In the multilayer printed wiring board 100A shown in fig. 1(f), a plurality of conductor patterns 107 are provided in layers on a substrate having a conductor pattern 102 on the surface, and an interlayer insulating layer 103 is provided between the layers. The conductive pattern 102 on the substrate and the conductive pattern 107 of each layer are connected through the opening 104. A surface protective film 108 is provided on the surface of the multilayer printed wiring board, and at least one of the surface protective film 108 and the interlayer insulating layer 103 is formed using the photosensitive resin composition of the present embodiment or the photosensitive resin film of the present embodiment.

The multilayer printed wiring board 100A can be obtained by, for example, laminating a copper-clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a conductor pattern by an etching method or a semi-additive method. Hereinafter, a method for manufacturing the multilayer printed wiring board 100A will be briefly described with reference to fig. 1.

First, interlayer insulating layers 103 are formed on both surfaces of a copper-clad laminate 101 having conductor patterns 102 on both surfaces (see fig. 1 a). The interlayer insulating layer 103 is formed by the method described in the method for manufacturing a printed wiring board, that is: the photosensitive resin composition of the present embodiment is applied or the photosensitive resin film of the present embodiment is thermally laminated using a laminator to form a photosensitive layer, and the photosensitive layer is cured by exposing a region other than a portion that needs to be electrically connected to the outside (a conductor pattern of another layer) to light using a negative film, and the unexposed portion is removed (see fig. 1 (b)). The interlayer insulating layer 103 is a film having an opening 104. Here, the smear (residue) existing around the opening 104 may be removed by desmear treatment or plasma etching.

Next, a conductor pattern 107 is formed. The conductor pattern 107 can be formed by, for example, a semi-additive method in which: a thin metal layer (seed layer) is formed, and a resin pattern (plating resist) is formed, followed by forming a conductor layer by an electroplating method, removing the resin pattern, and removing the seed layer by etching. Specifically, a seed layer 105 is formed by sputtering on the interlayer insulating layer 103 and on the conductor pattern 102 at the opening 104 (see fig. 1 (c)). The seed layer 105 can be formed by, for example, copper plating by sputtering. A photosensitive layer is formed on the seed layer 105 using a photosensitive resin composition for semi-addition, and a predetermined portion is exposed and developed using a negative film to form a resin pattern 106 having a predetermined pattern (see fig. 1 (d)).

Next, a conductive pattern 107 is formed by electroplating on a portion of the seed layer 105 where the resin pattern 106 is not formed, the resin pattern 106 is removed by a stripping liquid, and the seed layer 105 is removed by etching (see fig. 1 (e)).

By repeating the operations shown in fig. 1(b) to (e), the conductor pattern 107 is formed with a desired number of layers, and the surface protective film (permanent mask resist) 108 formed of the cured product of the photosensitive resin composition according to the present embodiment is formed on the outermost surface, whereby the multilayer printed wiring board 100A can be produced (see fig. 1 (f)). Here, for example, the photosensitive resin composition according to the present embodiment can be used as the photosensitive resin composition for semi-addition.

The multilayer printed wiring board 100A obtained by the operation described above can mount semiconductor elements at corresponding locations and ensure electrical connection.

In the printed wiring board according to the present embodiment, at least one of the surface protective film and the interlayer insulating layer uses the photosensitive resin composition according to the present embodiment or the photosensitive resin film made of the photosensitive resin composition, and thus the photosensitive resin composition according to the present embodiment can have the advantages of excellent adhesion to the inner layer circuit and resolution.

Further, with the trend toward smaller and higher performance electronic devices, there is a remarkable tendency toward higher density of semiconductor chips due to narrower pitches of conductor patterns, and as a semiconductor mounting method for coping with this tendency, a flip chip connection method of bonding a semiconductor chip and a substrate by solder bumps has become mainstream, but there have been some problems as follows in the past.

The flip chip connection method is a semiconductor mounting method using a reflow method in which solder balls are arranged between a substrate and a semiconductor chip and the entire body is heated and fusion-bonded. Therefore, during reflow, the substrate itself is exposed to a high-temperature environment, and a large stress is generated in a solder ball connecting the substrate and the semiconductor due to thermal shrinkage of the substrate, which may cause poor connection of the conductor pattern and cracking (cracking) of the surface protective film or the underfill. In addition, since the substrate is exposed to a high-temperature environment, a large stress may be generated at the connection interface due to thermal expansion of the resin composition for forming the surface protective film or the like provided on the substrate, and a connection failure may occur. The photosensitive resin composition according to the present embodiment has excellent heat resistance in addition to excellent adhesion to an inner layer circuit, resolution, and adhesion to a chip component, and has sufficient performance to solve these problems. Therefore, the printed wiring board according to the present embodiment is less likely to cause connection failure of the conductor pattern, cracking of the surface protective film, and the like, and has high quality.

[ semiconductor Package ]

The present invention also provides a semiconductor package in which the semiconductor element is mounted on the 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 on a predetermined position of the printed wiring board of the present invention, and sealing the semiconductor element with a sealing resin or the like.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited to these examples.

The photosensitive resin compositions obtained in the respective examples were evaluated for properties by the following methods.

[1. evaluation of resolution ]

A copper-clad laminate having a thickness of 1.0mm (product name "MCL-E-67" from Hitachi chemical Co., Ltd.) was prepared, the protective film was peeled off from the photosensitive resin film with the carrier film and protective film produced in each example, and the exposed photosensitive resin film was laminated on the copper-clad laminate using a pressure type vacuum laminator (product name "MVLP-500" from Hitachi chemical Co., Ltd.) under predetermined lamination conditions (pressure bonding pressure: 0.4MPa, pressure heating plate temperature: 80 ℃, evacuation time: 25 seconds, lamination pressure time: 25 seconds, air pressure: 4kPa or less) to obtain a laminate having a photosensitive layer.

Then, via hole patterns having a predetermined opening diameter (opening mask diameter size: 5, 8, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, and) Using an i-line exposure apparatus (model: UX-2240SM-XJ-01, manufactured by USHIO Co., Ltd.) and having a thickness of 50 to 1000mJ/cm²In the range of 50mJ/cm per change²The photosensitive layer is exposed.

Then, a1 mass% aqueous solution of sodium carbonate was used at 1.765 × 10⁵The spray development was carried out under a pressure of Pa for a time equivalent to 2 times the shortest development time (shortest time for the unexposed portions of the photosensitive layer to be removed) at 30 ℃.

Next, an ultraviolet exposure apparatus was used at a dose of 2,000mJ/cm²After exposure with the exposure amount of (2), the copper-clad laminate was heated at 160 ℃ for 1 hour to prepare a test piece having a cured film provided with a through-hole pattern of a predetermined size on the copper-clad laminate substrate.

The test piece was observed with a metal microscope, and the minimum mask diameter of the mask diameters in which the openings were confirmed was set as the minimum opening mask diameter, and evaluated according to the following criteria.

< evaluation Standard >

A: the minimum aperture mask diameter is less than or equal to 15 μm.

B: the minimum aperture mask diameter exceeds 15 μm and is less than or equal to 50 μm.

C: the minimum aperture mask diameter exceeds 50 μm.

[2 evaluation of adhesion to inner layer Circuit ]

(1) Preparation of microetching solution

The respective components were mixed in accordance with the compositions shown in Table 1 to prepare microetching agents (aqueous solutions). The balance of each formulation shown in table 1 was ion-exchanged water.

[ Table 1]

TABLE 1

(2) Preparation of measurement sample

At a thickness of 35 μmThe electrolytic copper foil of (2) was subjected to electrolytic copper plating to obtain a test piece, and a microetching agent (composition 1 or composition 2) shown in Table 1 was sprayed onto the plating surface of the test piece at 25 ℃ under a spray pressure of 0.05MPa, and etching was performed while adjusting the etching time so that the etching amount became 0.1. mu.m. Subsequently, the etching-treated surface was washed with water, sprayed with a 3.5 mass% hydrochloric acid aqueous solution at a temperature of 25 ℃ for 10 seconds, washed with water, and dried. The photosensitive resin films prepared in the respective examples from which the protective film was peeled were laminated on the etched surfaces of the respective copper foils after drying, and exposed to light (exposure conditions: 2,000 mJ/cm)²) And curing (curing conditions: 160 ℃ for 1 hour) to form a composite having a cured film obtained by curing the photosensitive resin film on the surface. Preparation of the complex: a composite for measuring peel strength after moisture absorption deterioration test; and a composite for measuring the peel strength without performing a moisture absorption deterioration test.

(3) Moisture absorption deterioration test

The composite obtained above was put into a high accelerated life test (HAST) apparatus at 130 ℃ and 85% humidity for 50 hours, and subjected to moisture absorption treatment.

(4) Measurement of peeling Strength

The peel strength of each of the composite not subjected to moisture absorption treatment and the composite subjected to moisture absorption treatment was measured by the following method.

After a copper-clad laminate having a thickness of 1.6mm as a back sheet was adhered to a cured film of the composite with an adhesive (product name "bond E set" manufactured by Konishi Co., Ltd.), only the copper foil portion of the test piece was cut into a line shape having a width of 1 cm. Then, the peel strength between the copper foil and the cured film of the test piece cut into a line shape was measured according to JIS C6481, and evaluated based on the following criteria.

< evaluation Standard >

A: the peel strength is greater than or equal to 0.5 kN/m.

B: the peel strength is greater than or equal to 0.3kN/m and less than 0.5 kN/m.

C: the peel strength is less than 0.3 kN/m.

(Synthesis example 1 Synthesis of acid-modified epoxy acrylate resin A-1)

A dicyclopentadiene type epoxy resin (product name "XD-1000" manufactured by Nippon Kagaku K.K.), 250 parts by mass of an epoxy resin having a structure represented by the general formula (A-2) [ (a1) component ], 70 parts by mass of an acrylic acid [ (b) component ], 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were charged into a reaction vessel, and the mixture was heated to 90 ℃ and stirred to dissolve the mixture. Then, the obtained solution was cooled to 60 ℃,2 parts by mass of triphenylphosphine was added thereto, and the mixture was heated to 100 ℃ to react until the acid value of the solution became 1 mgKOH/g. To the reacted solution were added 98 parts by mass of tetrahydrophthalic anhydride (THPAC) [ (c) component ] and 850 parts by mass of carbitol acetate, and the mixture was heated to 80 ℃ to react for 6 hours. Then, the mixture was cooled to room temperature, and the solvent was distilled off, thereby obtaining a THPAC-modified dicyclopentadiene type epoxy acrylate (acid-modified epoxy acrylate resin a-1) as the (a) component having a solid content concentration of 65 mass%.

(Synthesis example 2 Synthesis of acid-modified epoxy acrylate resin A-2)

In a reaction vessel, 90 parts by mass of a dicyclopentadiene type epoxy resin (an epoxy resin having a structure represented by the above general formula (A-3) [ (a1) component ], 90 parts by mass of an acrylic acid [ (b) component ], 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate) (product name "ADEKA RESIN EP-4088L", manufactured by ADEKA Co., Ltd.), were charged, and the mixture was dissolved by heating to 90 ℃ and stirring. Then, the obtained solution was cooled to 60 ℃,2 parts by mass of triphenylphosphine was added thereto, and the mixture was heated to 100 ℃ to react until the acid value of the solution became 1 mgKOH/g. To the reacted solution were added 98 parts by mass of tetrahydrophthalic anhydride (THPAC) [ (c) component ] and 850 parts by mass of carbitol acetate, and the mixture was heated to 80 ℃ to react for 6 hours. Then, the reaction mixture was cooled to room temperature, and the solvent was distilled off, thereby obtaining a THPAC-modified dicyclopentadiene type epoxy acrylate (acid-modified epoxy acrylate resin a-2) as the (a) component having a solid content concentration of 65 mass%.

(Synthesis example 3 Synthesis of acid-modified epoxy acrylate resin A-3)

A bisphenol F novolak-type epoxy resin (trade name "EXA-7376" available from DIC Co., Ltd.) containing Y in the general formula (A-5) was charged into a reaction vessel^A8And Y^A9Is glycidyl and R^A3And R^A4A bisphenol F novolak type epoxy resin having a hydrogen atom-containing structural unit (component [ (a 2))])350 parts by mass of acrylic acid [ (b) component]70 parts by mass, 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate, and the mixture was dissolved by heating to 90 ℃ and stirring. Then, the obtained solution was cooled to 60 ℃,2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ℃ to react until the acid value of the solution became 1 mgKOH/g. Adding tetrahydrophthalic anhydride (THPAC) [ (c) component to the reacted solution]98 parts by mass and 850 parts by mass of carbitol acetate were heated to 80 ℃ to react for 6 hours. Then, it was cooled to room temperature, thereby obtaining a THPAC-modified bisphenol F novolak-type epoxy acrylate (acid-modified epoxy acrylate resin a-3) as the (a) component having a solid content concentration of 73 mass%.

Examples 1 to 6 and comparative examples 1 to 2

(1) Production of photosensitive resin composition

The compositions were prepared according to the formulation compositions shown in table 2 (the unit of the numerical values in the table is parts by mass, in the case of a solution, the amount is converted to solid content.) and kneaded using a three-roll mill. Then, methyl ethyl ketone was added so that the solid content concentration became 60 mass%, thereby obtaining a photosensitive resin composition.

(2) Production of photosensitive resin film

The photosensitive resin composition prepared in each example was coated on a carrier film of polyethylene terephthalate having a thickness of 16 μm (product name "G2-16" manufactured by Diman corporation) so that the dried film thickness became 10 μm, and was dried at 75 ℃ for 30 minutes by using a hot air convection dryer, thereby forming a photosensitive resin film (photosensitive layer). Next, a polyethylene film (product name "NF-15" from tamapol) was bonded as a protective film to the surface of the photosensitive resin film (photosensitive layer) opposite to the side in contact with the carrier film, thereby producing a photosensitive resin film to which the carrier film and the protective film were bonded.

Using the photosensitive resin film thus produced, each evaluation was performed according to the method described above. The results are shown in Table 2.

[ Table 2]

TABLE 2

The components used in each example are as follows.

[ (A) component ]

Acid-modified epoxy acrylate resin a-1: THPAC-modified dicyclopentadiene type epoxy acrylate (corresponding to the component (X); dicyclopentadiene skeleton content: 18% by mass) obtained in Synthesis example 1

Acid-modified epoxy acrylate resin a-2: THPAC-modified dicyclopentadiene type epoxy acrylate (corresponding to the component (X); dicyclopentadiene skeleton content: 22% by mass) obtained in Synthesis example 2

Acid-modified epoxy acrylate resin a-3: THPAC-modified bisphenol F novolak-type epoxy acrylate obtained in Synthesis example 3

[ (B) component ]

Photopolymerization initiator 1: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime)

Photopolymerization initiator 2: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone

Photopolymerization initiator 3: 2, 4-diethylthioxanthone

[ (C) ingredient ]

Dipentaerythritol hexaacrylate

Dicyclodecane dimethanol diacrylate (corresponding to the component (X); Dicyclopentadiene skeleton content: 44% by mass)

[ (D) component ]

Epoxy resin of tetramethyl biphenol type

Dicyclopentadiene type epoxy resin: manufactured by Nippon Chemicals K.K., trade name "XD-1000" (corresponding to the component (X); content of dicyclopentadiene skeleton: 31% by mass)

Epoxidized polybutadiene: trade name "PB-4700" made of Dacellosolve of Kyowa K.K "

[ (E) ingredient ]

Phthalocyanine-based pigment

[ (F) ingredient ]

Silica: manufactured by Longsen K.K., trade name "CRS-2101-41" and having an average particle diameter of 1.3 μm

[ (G) ingredient ]

Polyester-based elastomer: manufactured by Hitachi chemical Co., Ltd., trade name "Espel 1108"

[ (H) ingredient ]

Melamine

As is clear from table 2, the cured films formed from the photosensitive resin compositions of examples 1 to 6 of the present embodiment have good resolution, and the inner layer adhesion after the moisture absorption deterioration test is excellent at a peel strength of 0.3kN/m or more, and thus are particularly suitable as an interlayer insulating layer in a printed wiring board. In contrast, the resin compositions of comparative examples 1 to 2 did not have sufficient inner layer adhesion after the moisture absorption deterioration test.

Description of the symbols

100A: a multilayer printed wiring board; 102: a circuit pattern; 103: an interlayer insulating layer; 104: through holes (via holes); 105: a seed layer; 106: a resist pattern; 107: a copper circuit layer; 108: and a solder resist layer.