阅读说明：本技术 感光性树脂组合物、感光性树脂膜、多层印刷配线板和半导体封装体、以及多层印刷配线板的制造方法 (Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board ) 是由 冈出翔太 野本周司 铃木庆一 于 2019-05-31 设计创作，主要内容包括：本发明提供通孔分辨率、与镀铜的粘接强度、耐裂纹性和电绝缘可靠性优异的感光性树脂组合物、光通孔形成用感光性树脂组合物以及层间绝缘层用感光性树脂组合物。另外,还提供由上述感光性树脂组合物构成的感光性树脂膜和层间绝缘层用感光性树脂膜。进一步,还提供多层印刷配线板和半导体封装体,并提供上述多层印刷配线板的制造方法。具体而言,上述感光性树脂组合物为含有(A)具有乙烯性不饱和基的光聚合性化合物和(B)光聚合引发剂的感光性树脂组合物,上述(A)具有乙烯性不饱和基的光聚合性化合物包含(A1)具有乙烯性不饱和基并且具有酸性取代基和脂环式骨架的光聚合性化合物。(The invention provides a photosensitive resin composition, a photosensitive resin composition for forming an optical via, and a photosensitive resin composition for an interlayer insulating layer, which are excellent in via resolution, adhesion strength with copper plating, crack resistance, and electrical insulation reliability. Also disclosed are a photosensitive resin film comprising the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer. Further, a multilayer printed wiring board and a semiconductor package are provided, and a method of manufacturing the above multilayer printed wiring board is provided. Specifically, the photosensitive resin composition is a photosensitive resin composition containing (a) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator, and the (a) photopolymerizable compound having an ethylenically unsaturated group contains (a1) a photopolymerizable compound having an ethylenically unsaturated group, an acid substituent, and an alicyclic skeleton.)

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

the photopolymerizable compound (A) having an ethylenically unsaturated group includes (A1) a photopolymerizable compound having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton.

2. The photosensitive resin composition according to claim 1, wherein the (a) photopolymerizable compound having an ethylenically unsaturated group further comprises at least 1 selected from the group consisting of (Ai) a monofunctional vinyl monomer having 1 ethylenically unsaturated group capable of polymerization, (Aii) a difunctional vinyl monomer having 2 ethylenically unsaturated groups capable of polymerization, and (Aiii) a polyfunctional vinyl monomer having at least 3 ethylenically unsaturated groups capable of polymerization.

3. The photosensitive resin composition according to claim 1 or 2, wherein in the (A1) photopolymerizable compound having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton, the alicyclic skeleton is an alicyclic skeleton having 5 to 20 ring carbon atoms.

4. The photosensitive resin composition according to claim 1 or 2, wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton is characterized in that the alicyclic skeleton is composed of two or more rings.

5. The photosensitive resin composition according to claim 1,2 or 4, wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton has three rings in the alicyclic skeleton.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein in the (A1) photopolymerizable compound having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton, the alicyclic skeleton is represented by the following general formula (a),

[ solution 1]

In the general formula (a), R^A1M represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any position in the alicyclic skeleton¹Is an integer of 0 to 6, and is a binding site with other structures.

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton is represented by the following general formula (A-1),

[ solution 2]

In the general formula (A-1), R^A1An alkyl group having 1 to 12 carbon atoms, which may be substituted at any position in the alicyclic skeleton, R^A2Represents an alkyl group having 1 to 12 carbon atoms, R^A3Is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least 1R^A3Is an organic group having an ethylenically unsaturated group and an acidic substituent, m¹Is an integer of 0 to 6, m²Is an integer of 0 to 3, and n is 0 to 10.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the photopolymerizable compound (A1) has an ethylenically unsaturated group and has an acidic substituent and an alicyclic skeleton, and the acidic substituent is at least 1 selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group.

9. The photosensitive resin composition according to any one of claims 1 to 8, further comprising (C) a thermosetting resin.

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

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the elastomer (D) comprises at least 1 selected from the group consisting of styrene-based elastomers, olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic elastomers and silicone-based elastomers.

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

17. A multilayer printed wiring board comprising an interlayer insulating layer formed by using the photosensitive resin composition according to any one of claims 1 to 12.

18. A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to claim 15.

19. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board of claim 17 or 18.

20. A method for manufacturing a multilayer printed wiring board, comprising the following steps (1) to (4):

step (1): laminating the photosensitive resin film according to claim 15 on one or both surfaces of a circuit board;

step (2): a step of forming an interlayer insulating layer having a through hole by exposing and developing the photosensitive resin film laminated in the step (1);

step (3): a step of roughening the through hole and the interlayer insulating layer;

step (4): and forming a circuit pattern on the interlayer insulating layer.

Technical Field

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

Background

In recent years, electronic devices have been increasingly downsized and highly functional, and multilayer printed wiring boards have been increasingly densified due to an increase in the number of circuit layers and miniaturization of wiring. In particular, semiconductor package substrates such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted have been significantly increased in density, and in addition to miniaturization of wiring, thinning of an insulating film and further reduction in diameter of through holes (also referred to as "via holes") for interlayer connection have been required. In addition, along with the thinning of the insulating film in the printed wiring board, excellent electrical insulation reliability between layers [ particularly, electrical insulation reliability after moisture absorption (High Accelerated Stress Test) resistance) ] is also required.

As a method for manufacturing a printed wiring board, a method for manufacturing a multilayer printed wiring board using a build-up method (for example, see patent document 1) in which an interlayer insulating film and a conductor circuit layer are sequentially laminated is cited. With the miniaturization of circuits, semi-additive methods for forming circuits by plating have become the mainstream of multilayer printed wiring boards.

In the conventional semi-addition method, for example: (1) laminating a thermosetting resin film on a conductor circuit, and curing the thermosetting resin film by heating to form an interlayer insulating layer; (2) then, forming a through hole for interlayer connection by laser processing, and performing desmear treatment and roughening treatment by alkali permanganic acid treatment and the like; (3) thereafter, performing electroless copper plating treatment on the substrate, forming a pattern using a resist, and then performing electrolytic copper plating to form a copper circuit layer; (4) next, resist stripping was performed, and flash etching of the electroless layer was performed, thereby forming a copper circuit.

As described above, laser processing has been the mainstream as a method for forming a through hole in an interlayer insulating layer formed by curing a thermosetting resin film, but reduction in the diameter of the through hole by laser irradiation using a laser processing machine has reached the 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 need to be provided due to densification, a large amount of time is required to form the through holes, which causes a problem of poor manufacturing efficiency.

Under such circumstances, as a method capable of forming a plurality of through holes at a time, a method of forming a plurality of small-diameter through holes at a time by photolithography using a photosensitive resin composition containing (a) an acid-modified vinyl-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler and (E) a silane compound, wherein the content of the inorganic filler (D) is 10 to 80 mass% has been proposed (for example, see patent document 2).

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

Disclosure of Invention

Problems to be solved by the invention

Patent document 2 has solved one of the problems of suppressing the decrease in adhesion strength to copper plating due to the use of a photosensitive resin composition as a material of an interlayer insulating layer or a surface protective layer instead of a conventional thermosetting resin composition, and further has solved the problems of via resolution and adhesion to a substrate made of a silicon material and a chip component. However, in addition to further miniaturization of wiring, thinning of an insulating film and reduction in diameter of via holes for interlayer connection are also advancing, and thus, there is an increasing demand for improvement in adhesion strength with copper plating and electrical insulation reliability. Therefore, the photosensitive resin composition of patent document 2 still has room for further improvement in adhesion strength with copper plating and electrical insulation reliability.

Similarly, it is conceivable to use a photosensitive resin composition or the like, which has been conventionally used as a solder resist material, as a material for an interlayer insulating layer, but since characteristics (for example, electrical insulation reliability between layers, adhesion strength with copper plating, high heat resistance capable of withstanding multiple heating, high dimensional accuracy of a via shape, and the like) which are not required for a solder resist are required for the interlayer insulating layer, it is difficult to predict whether or not the interlayer insulating layer can withstand application as an interlayer insulating layer, and it is not easy to use the interlayer insulating layer.

Further, it is difficult to say that the conventional photosensitive resin composition has sufficient crack resistance to withstand reflow mounting.

Accordingly, an object of the present invention is to provide a photosensitive resin composition, a photosensitive resin composition for forming an optical via, and a photosensitive resin composition for an interlayer insulating layer, each of which has excellent via resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability. In addition, it also consists in: providing a photosensitive resin film comprising the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer; providing a multilayer printed wiring board and a semiconductor package; and a method for producing the multilayer printed wiring board.

Means for solving the problems

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by incorporating (a) and (B) components described later into a photosensitive resin composition, and that the (a) component contains "(a 1) a photopolymerizable compound having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton".

That is, the present invention relates to the following technologies [1] to [20 ].

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

the photopolymerizable compound (a) having an ethylenically unsaturated group includes (a1) a photopolymerizable compound having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton.

[2] The photosensitive resin composition according to the above [1], wherein the photopolymerizable compound (A) having an ethylenically unsaturated group further contains at least 1 selected from the group consisting of (Ai) a monofunctional vinyl monomer having 1 ethylenically unsaturated group capable of polymerization, (Aii) a difunctional vinyl monomer having 2 ethylenically unsaturated groups capable of polymerization, and (Aiii) a polyfunctional vinyl monomer having at least 3 ethylenically unsaturated groups capable of polymerization.

[3] The photosensitive resin composition according to the above [1] or [2], wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group, an acidic substituent, and an alicyclic skeleton, wherein the alicyclic skeleton is an alicyclic skeleton having 5 to 20 ring carbon atoms.

[4] The photosensitive resin composition according to the above [1] or [2], wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton has the alicyclic skeleton composed of two or more rings.

[5] The photosensitive resin composition according to the above [1], [2] or [4], wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and an acidic substituent and an alicyclic skeleton has the alicyclic skeleton composed of three rings.

[6] The photosensitive resin composition according to any one of the above [1] to [5], wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton, the alicyclic skeleton is represented by the following general formula (a),

[ solution 1]

(in the general formula (a), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. m is¹Is an integer of 0 to 6. Is a binding site to other structures. )

[7] The photosensitive resin composition according to any one of the above [1] to [6], wherein the photopolymerizable compound (A1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton is represented by the following general formula (A-1),

[ solution 2]

(in the general formula (A-1), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. R^A2Represents an alkyl group having 1 to 12 carbon atoms. R^A3Is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least 1R^A3An organic group having an ethylenically unsaturated group and an acidic substituent. m is¹Is an integer of 0 to 6, m²Is an integer of 0 to 3. n is 0 to 10. )

[8] The photosensitive resin composition according to any one of the above [1] to [7], wherein the photopolymerizable compound (A1) has an ethylenically unsaturated group and has an acidic substituent and an alicyclic skeleton, and the acidic substituent is at least 1 selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phenolic hydroxyl group.

[9] The photosensitive resin composition according to any one of the above [1] to [8], further comprising (C) a thermosetting resin.

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

[11] The photosensitive resin composition according to any one of the above [1] to [10], wherein the elastomer (D) contains at least 1 selected from the group consisting of styrene-based elastomers, olefin-based elastomers, polyester-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic elastomers and silicone-based elastomers.

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

[17] A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of the above [1] to [12 ].

[18] A multilayer printed wiring board comprising an interlayer insulating layer formed using the photosensitive resin film according to [15 ].

[19] A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board as recited in the above item [17] or [18 ].

[20] A method for manufacturing a multilayer printed wiring board, comprising the following steps (1) to (4):

a step (1) of laminating the photosensitive resin film according to [15] on one or both surfaces of a circuit board;

a step (2) of exposing and developing the photosensitive resin film laminated in the step (1) to form an interlayer insulating layer having a through hole;

a step (3) of roughening the through hole and the interlayer insulating layer;

and (4) forming a circuit pattern on the interlayer insulating layer.

Effects of the invention

According to the present invention, a photosensitive resin composition for forming an optical via, and a photosensitive resin composition for an interlayer insulating layer, which are excellent in via resolution, adhesion strength with copper plating, crack resistance, and electrical insulation reliability, can be provided. Further, a photosensitive resin film comprising the photosensitive resin composition and a photosensitive resin film for an interlayer insulating layer can be provided; a multilayer printed wiring board and a semiconductor package are provided, each of which includes an interlayer insulating layer formed using the photosensitive resin composition or the photosensitive resin film.

Further, it is possible to provide a method for efficiently manufacturing a multilayer printed wiring board having a high-resolution through-hole, high adhesion strength between an interlayer insulating layer and copper plating, and excellent reliability of electrical insulation. The multilayer printed wiring board obtained by the manufacturing method of the present invention has a through hole with a smaller diameter than a through hole formed by laser processing.

Drawings

Fig. 1 is a schematic diagram showing one embodiment of a process for manufacturing a multilayer printed wiring board according to the present embodiment.

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. The lower limit and the upper limit of the numerical range may be arbitrarily combined with the lower limit or the upper limit of another numerical range, respectively.

In the present specification, when there are a plurality of substances corresponding to each component in the content ratio of each component in the photosensitive resin composition, the total content ratio of the plurality of substances present in the photosensitive resin composition is referred to unless otherwise specified.

In the present specification, the "number of ring-forming carbon atoms" refers to the number of carbon atoms necessary for forming a ring, and does not include the number of carbon atoms of a substituent group of the ring. For example, the number of ring-forming carbon atoms of the cyclohexane skeleton and the methylcyclohexane skeleton is 6.

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

[ photosensitive resin composition, photosensitive resin composition for forming optical via hole, and photosensitive resin composition for interlayer insulating layer ]

A photosensitive resin composition according to an embodiment of the present invention (hereinafter, may be simply referred to as "the present embodiment") is a photosensitive resin composition containing (a) a photopolymerizable compound having an ethylenically unsaturated group and (B) a photopolymerization initiator, wherein the (a) photopolymerizable compound having an ethylenically unsaturated group includes (a1) a photopolymerizable compound having an ethylenically unsaturated group, an acid substituent, and an alicyclic skeleton.

In the present specification, the above components may be referred to as a component (a), a component (B), a component (a1), and the like, and the other components may be referred to as simply "components". In the present specification, the "resin component" refers to the above-mentioned component (a) and component (B), and optionally contains other components (for example, components (C), (D), (E) and (H)), but does not contain the inorganic filler (F) and the pigment (G), which may be contained as required, which will be described later. The "solid component" is a nonvolatile component excluding volatile substances such as water and a solvent contained in the photosensitive resin composition, and means a component remaining without volatilization at the time of drying the resin composition, and also includes a component which is liquid, syrup-like, or wax-like at room temperature around 25 ℃.

The photosensitive resin composition of the present embodiment is suitable for forming a through hole by photolithography (also referred to as "through-hole formation"), and therefore the present invention also provides a photosensitive resin composition for forming a through-hole. The photosensitive resin composition of the present embodiment is excellent in via hole resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability, and is useful as an interlayer insulating layer of a multilayer printed wiring board. 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 may contain will be described in detail.

[ A ] photopolymerizable compound having ethylenically unsaturated group >

The photosensitive resin composition of the present embodiment contains a photopolymerizable compound having an ethylenically unsaturated group as the component (a). Examples of the ethylenically unsaturated group contained in the component (a) include: vinyl, allyl, propargyl, butenyl, ethynyl, phenylethynyl, maleimido, nadimidyl, (meth) acryloyl, and the like. The ethylenically unsaturated group is preferably a (meth) acryloyl group.

In the present invention, the component (a) includes a photopolymerizable compound (a1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton, which will be described later. (A) The component (a1) is contained, whereby the photosensitive resin composition is excellent in via resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability.

Hereinafter, component (a1) will be described in detail.

((A1) photopolymerizable compound having an ethylenically unsaturated group, an acidic substituent and an alicyclic skeleton)

The ethylenically unsaturated group contained in component (a1) includes the same groups as those of the above ethylenically unsaturated group, and is preferably at least 1 selected from the group consisting of a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimido group and a (meth) acryloyl group, more preferably a vinyl group, an allyl group and a (meth) acryloyl group, and still more preferably a (meth) acryloyl group.

The acidic substituent of the component (a1) is preferably at least 1 selected from the group consisting of a carboxyl group, a sulfonic acid group, a phenolic hydroxyl group and the like, and more preferably a carboxyl group.

The alicyclic skeleton contained in the component (A1) is preferably an alicyclic skeleton having 5 to 20 ring-forming carbon atoms, more preferably an alicyclic skeleton having 5 to 18 ring-forming carbon atoms, still more preferably an alicyclic skeleton having 6 to 18 ring-forming carbon atoms, particularly preferably an alicyclic skeleton having 8 to 14 ring-forming carbon atoms, and most preferably an alicyclic skeleton having 8 to 12 ring-forming carbon atoms, from the viewpoints of resolution of through holes, adhesion strength with copper plating, crack resistance, and electrical insulation reliability.

In view of the resolution of through holes, the adhesion strength to copper plating, the crack resistance, and the electrical insulation reliability, the alicyclic skeleton is preferably composed of 2 or more rings, more preferably 2 to 4 rings, and still more preferably 3 rings. Examples of the alicyclic skeleton having 2 or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a saturated dicyclopentadiene skeleton.

The alicyclic skeleton is preferably a saturated dicyclopentadiene skeleton, and more preferably an alicyclic skeleton represented by the following general formula (a) (saturated dicyclopentadiene skeleton) from the viewpoints of via resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability.

[ solution 3]

(in the general formula (a), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. m is¹Is an integer of 0 to 6. Is a binding site to other structures. )

In the general formula (a), as R^A1Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl groups. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

m¹Is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0.

m¹When the number is an integer of 2 to 6, a plurality of R^A1May be the same or different. Further, a plurality of R^A1To the extent possible, may be substituted on the same carbon atom, or on different carbon atoms.

The bond site to another structure may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to a carbon atom represented by 1 or 2 and a carbon atom represented by any one of 3 to 4 in the following general formula (a').

[ solution 4]

(in the general formula (a'), R^A1、m¹And is the same as in formula (a). )

The component (a1) is preferably an acid-modified epoxy derivative containing an alicyclic skeleton and an ethylenically unsaturated group (a1-1) obtained by reacting (A3) a saturated or unsaturated group-containing polybasic acid anhydride with (a2) an ethylenically unsaturated group-containing organic acid to modify (a1) an epoxy resin containing an alicyclic skeleton [ hereinafter, sometimes referred to as component (a') ], from the viewpoints of enabling alkaline development and being excellent in via hole resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability.

- (a1) epoxy resin containing alicyclic skeleton

The epoxy resin having an alicyclic skeleton (a1) is preferably an epoxy resin having 2 or more epoxy groups. Epoxy resins can be classified as: glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and the like. Among them, glycidyl ether type epoxy resins are preferable.

In the present invention, as the epoxy resin, at least an epoxy resin having an alicyclic skeleton is used. The alicyclic skeleton is described in the same manner as the alicyclic skeleton contained in the component (a1), and the preferable embodiment is also the same.

The epoxy resin having an alicyclic skeleton (a1) is preferably an epoxy resin represented by the following general formula (a 1-1). Further, an epoxy resin having a structural unit represented by the following general formula (a1-2) is also preferable.

[ solution 5]

(in the general formula (a1-1), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. R^A2Represents an alkyl group having 1 to 12 carbon atoms. m is¹Is an integer of 0 to 6, m²Is an integer of 0 to 3. n is 0 to 10. )

[ solution 6]

(in the general formula (a1-2), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. m is¹Is an integer of 0 to 6. )

In the general formula (a1-1) and the general formula (a1-2), R^A1And R in the general formula (a)^A1Likewise, the preferred mode is the same.

As R in the general formula (a1-1)^A2Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl groups. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

M in the general formula (a1-1) and the general formula (a1-2)¹And m in the general formula (a)¹Likewise, the preferred mode is the same.

M in the formula (a1-1)²Is an integer of 0 to 3, preferably 0 or 1, more preferably 0.

N in the general formula (a1-1) represents the number of repeating structural units in parentheses, and is 0 to 10. The epoxy resin is usually a mixture of substances differing in the number of repetitions of the structural unit in parentheses, and therefore in this case, n represents the average value of the mixture. The number n is preferably 2 to 10.

As the (a1) alicyclic skeleton-containing epoxy resin, commercially available products can be used, and examples thereof include XD-1000 (trade name, manufactured by Nippon Kagaku K.K.), EPICLON HP-7200L, EPICLON HP-7200HH, EPICLON HP-7200HHH (trade name, "EPICLON" is a registered trademark, manufactured by DIC).

As the epoxy resin (a1), an epoxy resin other than the epoxy resin having an alicyclic skeleton (hereinafter, may be referred to as another epoxy resin) may be used in combination. Examples of other epoxy resins include: 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; biphenyl aralkyl type epoxy resins; a stilbene type epoxy resin; naphthalene type epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthol novolac type epoxy resins, naphthol aralkyl type epoxy resins, and naphthylene ether type epoxy resins; biphenyl type epoxy resin; a xylylene type epoxy resin; a dihydroanthracene type epoxy resin; an aliphatic chain epoxy resin; rubber-modified epoxy resins, and the like.

- (a2) organic acid containing ethylenically unsaturated group

The organic acid having an ethylenically unsaturated group (a2) is not particularly limited, but is preferably a monocarboxylic acid having an ethylenically unsaturated group. The ethylenically unsaturated group is as described for the ethylenically unsaturated group in the component (A1).

Examples of the monocarboxylic acid having an ethylenically unsaturated group include: acrylic acid derivatives such as acrylic acid, 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 monoglycidyl ethers containing ethylenically unsaturated groups or monoglycidyl esters containing ethylenically unsaturated groups and dibasic acid anhydrides. Among them, acrylic acid is preferable.

(a2) 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 a hydroxyl group-containing acrylate, an ethylenically unsaturated group-containing monoglycidyl ether or an ethylenically unsaturated group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio.

Examples of the hydroxyl group-containing acrylate, the monoglycidyl ether containing an ethylenically unsaturated group, and the monoglycidyl ester containing an ethylenically unsaturated group, which are used for synthesizing the half-ester compound as one example of the component (a2), include: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethylacrylate, glycidyl acrylate, glycidyl methacrylate, and the like.

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.

Although not particularly limited, in the reaction of the component (a1) and the component (a2), the reaction is preferably carried out at a ratio of 0.6 to 1.05 equivalents of the component (a2) to 1 equivalent of the epoxy group of the component (a1), and the reaction may be carried out at a ratio of 0.8 to 1.0 equivalent. By performing the reaction at such a ratio, the photopolymerization property, that is, the photosensitivity becomes high, and the via resolution tends to be improved.

The component (a1) and the component (a2) can be dissolved in an organic solvent to react with each other.

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.

Further, in order to promote the reaction between the component (a1) and the component (a2), a catalyst 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 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 component (a1) and the component (a 2). When the amount is the above amount, the reaction between the component (a1) and the component (a2) tends to be accelerated.

In addition, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like.

When a polymerization inhibitor is used, the amount thereof 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 component (a1) and the component (a2), from the viewpoint of improving the storage stability of the composition.

From the viewpoint of productivity, the reaction temperature of the component (a1) and the component (a2) is preferably 60 to 150 ℃, more preferably 70 to 120 ℃, and still more preferably 80 to 110 ℃.

The component (a') obtained by reacting the component (a1) with the component (a2) in this way is assumed to be a component having a hydroxyl group formed by a ring-opening addition reaction of an epoxy group of the component (a1) and a carboxyl group of the component (a 2).

- (a3) polybasic acid anhydrides-

The component (a3) may contain a saturated group or an unsaturated group. Examples of the component (a3) include: succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, itaconic anhydride, and the like. Among them, tetrahydrophthalic anhydride is preferable from the viewpoint of through hole resolution.

Presume that: by further reacting the component (A3) containing a saturated group or an unsaturated group with the component (a ') obtained above, the hydroxyl group (including the hydroxyl group originally present in the component (a 1)) of the component (a') is half-esterified with the acid anhydride group of the component (A3), and thereby (a1-1) an acid-modified epoxy derivative containing an ethylenically unsaturated group and an alicyclic skeleton is formed.

In the reaction of the component (a ') and the component (A3), the acid value of the acid-modified epoxy derivative containing an ethylenically unsaturated group and an alicyclic skeleton (a1-1) can be adjusted by, for example, reacting 0.1 to 1.0 equivalent of the component (A3) with respect to 1 equivalent of the hydroxyl group in the component (a').

(A1-1) the acid-modified epoxy derivative having an ethylenically unsaturated group and an alicyclic skeleton preferably has an acid value of 20 to 150mgKOH/g, more preferably 30 to 120mgKOH/g, and still more preferably 40 to 100 mgKOH/g. When the acid value is 20mgKOH/g or more, the solubility of the photosensitive resin composition in a dilute alkali solution tends to be excellent, and when the acid value is 150mgKOH/g or less, the electrical characteristics of the cured film tend to be improved.

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

The photopolymerizable compound (a1) having an ethylenically unsaturated group and having an acidic substituent and an alicyclic skeleton is not particularly limited, and is preferably represented by the following general formula (a-1).

[ solution 7]

(in the general formula (A-1), R^A1Represents an alkyl group having 1 to 12 carbon atoms, and may be substituted at any position of the alicyclic skeleton. R^A2Represents an alkyl group having 1 to 12 carbon atoms. R^A3Is an organic group having an ethylenically unsaturated group, an organic group having an ethylenically unsaturated group and an acidic substituent, or a glycidyl group, and at least 1R^A3An organic group having an ethylenically unsaturated group and an acidic substituent. m is¹Is an integer of 0 to 6, m²Is an integer of 0 to 3. n is 0 to 10. )

R in the above general formula (A-1)^A1、R^A2、m¹、m²And n is the same as in the above general formula (a1-1), and the preferable mode is also the same.

R^A3As shown in the above definition, is defined as: it is also considered that a part of the glycidyl groups in the general formula (a1-1) is unreacted, corresponding to the sites formed by the reaction of the glycidyl groups with the component (a2) and the component (a 3). That is, as R^A3The "organic group having an ethylenically unsaturated group" in the item(s) of (1) is a group derived from the above-mentioned component (a2), and the "organic group having an ethylenically unsaturated group and an acidic substituent" is a group derived from the above-mentioned components (a2) and (a3), provided that the above-mentioned components (a2) and (a3) react with all of the glycidyl groups in the above-mentioned general formula (a1-1)Oil-based reaction, then R^A3The "organic group having an ethylenically unsaturated group and an acidic substituent" may be the "organic group having an ethylenically unsaturated group" in a portion which reacts with only the component (a2), and the "glycidyl group" in a portion which does not react with either of the components (a2) and (a 3).

(molecular weight of (A1) photopolymerizable compound having ethylenically unsaturated group, acidic substituent and alicyclic skeleton)

(A1) The weight average molecular weight (Mw) of the component (B) is preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and still more preferably 3,000 to 18,000. When the amount is within this range, the adhesion strength with copper plating, heat resistance and electrical insulation reliability are improved. In particular, the weight average molecular weight (Mw) of the acid-modified epoxy derivative having an ethylenically unsaturated group and an alicyclic skeleton (A1-1) is preferably within the above range. Here, in the present specification, the weight average molecular weight is a value measured by Gel Permeation Chromatography (GPC) (manufactured by tokyo co., ltd.) using a standard curve of standard polystyrene, more specifically, a value measured by the method described below.

< 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

(A2-1) acid-modified ethylenically unsaturated group-containing epoxy derivative having no alicyclic skeleton)

The photopolymerizable compound (a) having an ethylenically unsaturated group may be further an embodiment including "(a 2-1) an acid-modified ethylenically unsaturated group-containing epoxy derivative having no alicyclic skeleton" obtained by reacting (a23) a saturated group-or unsaturated group-containing polybasic acid anhydride with (a22) an epoxy resin (a21) which does not contain an alicyclic skeleton and a compound obtained by modifying (a22) an ethylenically unsaturated group-containing organic acid.

The epoxy resin (a21) is not particularly limited as long as it is an epoxy resin not containing an alicyclic skeleton, and examples thereof include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among them, glycidyl ether type epoxy resins are preferable.

In addition, the above-mentioned (a21) epoxy resin can be classified into various epoxy resins according to the difference in the main skeleton, and among the above-mentioned various types of epoxy resins, it can be further classified as follows. 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; an aliphatic chain epoxy resin; rubber-modified epoxy resins, and the like. Among them, bisphenol novolac epoxy resins are preferable, and bisphenol F novolac epoxy resins are more preferable.

The preferable embodiments of the (a22) ethylenically unsaturated group-containing organic acid and the (a23) saturated or unsaturated group-containing polybasic acid anhydride are the same as those described for the (a2) ethylenically unsaturated group-containing organic acid and the (a3) saturated or unsaturated group-containing polybasic acid anhydride.

As a method of reacting the component (a23) with the compound obtained by modifying the component (a21) with the component (a22), a method of reacting the component (a3) with the compound obtained by modifying the component (a1) with the component (a2) can be referred to.

As the acid-modified ethylenically unsaturated group-containing epoxy derivative not having an alicyclic skeleton (A2-1), commercially available products can be used, and examples of the commercially available products include: CCR-1218H, CCR-1159H, CCR-1222H, PCR-1050, TCR-1335H, ZAR-1035, ZAR-2001H, UXE-3024, ZFR-1185, ZCR-1569H, ZXR-1807, ZCR-6000, and ZCR-8000 (trade name, manufactured by Nippon chemical Co., Ltd.); UE-9000, UE-EXP-2810PM, and UE-EXP-3045 (trade name, available from DIC corporation).

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

((A2-2) styrene-maleic acid resin)

The photopolymerizable compound (a) having an ethylenically unsaturated group may be used in combination with "(a 2-2) styrene-maleic acid resin", such as a hydroxyethyl (meth) acrylate-modified styrene-maleic anhydride copolymer ". The component (A2-2) does not contain an alicyclic skeleton. The component (A2-2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

((A2-3) epoxy polyurethane resin)

Further, as the photopolymerizable compound having an ethylenically unsaturated group (a), it is also possible to use in combination "(a 2-3) epoxy urethane resin obtained by reacting an isocyanate compound with a component (a') obtained by modifying the above-mentioned epoxy resin (a21) with an organic acid having an ethylenically unsaturated group (a 22). The component (A2-3) does not contain an alicyclic skeleton. The component (A2-3) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(component (A) other than the above)

From the viewpoint of improving chemical resistance after curing (exposure) and increasing the difference in developing solution resistance between exposed portions and unexposed portions, the photopolymerizable compound having an ethylenically unsaturated group (a) preferably further contains at least 1 selected from the group consisting of (Ai) a monofunctional vinyl monomer having 1 polymerizable ethylenically unsaturated group, (Aii) a difunctional vinyl monomer having 2 polymerizable ethylenically unsaturated groups, and (Aiii) a polyfunctional vinyl monomer having at least 3 polymerizable ethylenically unsaturated groups, and more preferably contains the component (Aiii). The components (Ai) to (Aiii) preferably have a molecular weight of 1,000 or less. In the present invention, the components (Ai) to (Aiii) do not include the component (a 1).

((Ai) monofunctional vinyl monomer)

Examples of the monofunctional vinyl monomer having 1 polymerizable ethylenically unsaturated group include (meth) acrylic acid, alkyl (meth) acrylate, and the like. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and hydroxyethyl (meth) acrylate. The component (Ai) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

((Aii) difunctional vinyl monomer)

Examples of the above-mentioned difunctional vinyl monomer having 2 polymerizable ethylenically unsaturated groups include polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-bis (4- (meth) acryloyloxypolyethoxypolypropoxyphenyl) propane, bisphenol a diglycidyl ether di (meth) acrylate, and the like. The component (Aii) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

((Aiii) polyfunctional vinyl monomer)

Examples of the polyfunctional vinyl monomer having at least 3 polymerizable ethylenically unsaturated groups include: a (meth) acrylate compound having a skeleton derived from trimethylolpropane, such as trimethylolpropane tri (meth) acrylate; (meth) acrylate compounds having a skeleton derived from tetramethylolmethane, such as tetramethylolmethane tri (meth) acrylate and tetramethylolmethane tetra (meth) acrylate; (meth) acrylate compounds having a skeleton derived from pentaerythritol, such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; (meth) acrylate compounds having a skeleton derived from dipentaerythritol, such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate; a (meth) acrylate compound having a skeleton derived from ditrimethylolpropane, such as ditrimethylolpropane tetra (meth) acrylate; (meth) acrylate compounds having a skeleton derived from diglycerin, and the like. Among them, from the viewpoint of improving chemical resistance after curing (exposure) and making a difference in developing solution resistance between exposed portions and unexposed portions large, a (meth) acrylate compound having a skeleton derived from dipentaerythritol is preferable, and dipentaerythritol penta (meth) acrylate is more preferable. The component (Aiii) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Here, the "(meth) acrylate compound having a skeleton derived from XXX" (where XXX is a compound name) refers to an esterified product of XXX and (meth) acrylic acid, and the esterified product also includes a compound modified with an alkyleneoxy group.

(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 55% by mass, further preferably 20 to 50% by mass, particularly preferably 25 to 50% by mass, and most preferably 30 to 45% by mass based on the total solid content of the photosensitive resin composition, from the viewpoints of heat resistance, electrical characteristics, and chemical resistance.

The component (a) is not particularly limited, and from the viewpoint of photosensitive characteristics, it is preferable to use the component (a1) and the component (Aiii) in combination. In this case, the content ratio [ (a1)/(Aiii) ] (mass ratio) of the component (a1) to the component (Aiii) is preferably 2 to 20, more preferably 2 to 15, further preferably 2.5 to 10, and particularly preferably 3 to 8.

The content ratio of the component (a1) to the total amount of the component (a) is preferably 20 to 95% by mass, more preferably 40 to 90% by mass, even more preferably 55 to 90% by mass, and particularly preferably 70 to 90% by mass, from the viewpoints of via hole resolution, adhesion strength to copper plating, crack resistance, and electrical insulation reliability.

[ photopolymerization initiator (B) ]

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

Examples of the component (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' -methyldiphenyl sulfide; acridines such as 9-phenylacridine and 1, 7-bis (9, 9' -acridinyl) heptane; acylphosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide; oxime esters such as 1, 2-octanedione-1- [4- (phenylthio) -phenyl-2- (O-benzoyloxime) ], 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethanone 1- (O-acetyloxime), and 1-phenyl-1, 2-propanedione-2- [ O- (ethoxycarbonyl) oxime ]. Among them, acetophenones and thioxanthones are preferable, and 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone and 2, 4-diethylthioxanthone are more preferable. Acetophenones have an advantage that they are not easily volatilized and are not easily generated as an outgas, and thioxanthones have an advantage that they can be photocured even in a visible light region.

(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, it is preferable to use acetophenone and thioxanthone in combination, and it is more preferable to use 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone and 2, 4-diethylthioxanthone in combination.

(content of component (B))

(B) The content of the component is not particularly limited, but is preferably 0.1 to 15% by mass, more preferably 0.15 to 5% by mass, further preferably 0.2 to 1.5% by mass, and particularly preferably 0.2 to 0.8% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (B) is 0.1 mass% or more, the possibility of elution of the exposed portion during development tends to be reduced in the interlayer insulating layer formed using the photosensitive resin composition, and if it is 15 mass% or less, the heat resistance tends to be improved.

[ B') photopolymerization initiation assistant >

The photosensitive resin composition of the present embodiment may contain both the component (B) and the photopolymerization initiation assistant (B'). Examples of the photopolymerization initiation assistant (B') include: tertiary amines such as ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine. The component (B') may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the photosensitive resin composition of the present embodiment contains the component (B'), the content thereof is preferably 0.01 to 20% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.3 to 2% by mass, based on the total amount of the resin components of the photosensitive resin composition. The photosensitive resin composition of the present embodiment may not contain the component (B').

< C thermosetting resin >

The photosensitive resin composition of the present embodiment may further contain a thermosetting resin as the component (C), and is preferably contained. (C) Component (C) is said to have no ethylenically unsaturated group because component (C) does not contain a substance corresponding to component (A). In addition, a substance having an epoxy group is contained in the component (C) in addition to satisfying the above condition.

The photosensitive resin composition of the present embodiment contains the thermosetting resin (C), and thus not only the adhesion strength to copper plating and the insulation reliability are improved, but also the heat resistance tends to be improved.

Examples of the thermosetting resin 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.

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

The epoxy resin is preferably an epoxy resin having 2 or more epoxy groups. Epoxy resins can be divided into: glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, 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; a spiro-containing epoxy resin; cyclohexane dimethanol type epoxy resins; a trimethylol type epoxy resin; an aliphatic chain epoxy resin; rubber-modified epoxy resins, and the like.

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

Among them, in particular, from the viewpoint of heat resistance, electrical insulation reliability, and adhesion strength with copper plating, bisphenol type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxy resins, naphthylene ether type epoxy resins, and cresol novolac 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.

Commercially available products may be used as these, and examples thereof include: bisphenol a type epoxy resin ("jER 828 EL", "YL 980" manufactured by mitsubishi chemical corporation), bisphenol F type epoxy resin ("jER 806H" manufactured by mitsubishi chemical corporation and "YL 983U", naphthalene type epoxy resin ("HP 4032D" and "HP 4710" manufactured by DIC corporation), naphthalene skeleton-containing type polyfunctional epoxy resin ("NC 7000" manufactured by nipponica), naphthol type epoxy resin ("ESN-475V" manufactured by hitachi chemical corporation), epoxy resin having a biphenyl structure ("NC 3000H" and "NC 3500" manufactured by nipponica chemical corporation, "YX 4000 HK" and "YL 6121" manufactured by mitsubishi chemical corporation), anthracene type epoxy resin ("YX 8800" manufactured by mitsubishi chemical corporation, glycerol type epoxy resin ("ZX 2" manufactured by mitsubishi chemical corporation), naphthylene type epoxy resin ("exx 4G 26" manufactured by mitsubishi chemical corporation, glycerol type epoxy resin ("exx 4G 7326" manufactured by mitsubishi chemical corporation, And cresol novolak type epoxy resin ("EPICLON-680" manufactured by DIC corporation).

As the epoxy resin, epoxy-modified polybutadiene can be used in addition to the above examples. In particular, from the viewpoint of workability in manufacturing 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 (C), and from this viewpoint, it is preferable to use the above-mentioned epoxy resin (aromatic epoxy resin that is solid at room temperature) and epoxy-modified polybutadiene (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 (C-1) from the viewpoints of adhesion strength to copper plating, heat resistance, thermal expansion coefficient and flexibility.

[ solution 8]

(in the general formula (C-1), a, b and C each represent a ratio of a structural unit 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 (C-1), the connection order of the respective structural units in parentheses is not specifically defined. 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 strength with copper plating, 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 (C-1), examples of commercially available epoxidized polybutadiene having an integer of a ═ 0.20, b ═ 0.20, C ═ 0.60, and y ═ 10 to 250 include "Epolead (registered trademark) PB 3600" (manufactured by cellosolve corporation).

(content of component (C))

When the photosensitive resin composition of the present embodiment contains the component (C), the content thereof 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. When the content of the component (C) is 5% by mass or more, the photosensitive resin composition can be sufficiently crosslinked, and the adhesion strength with copper plating and the electrical insulation reliability tend to be improved. On the other hand, if less than or equal to 70 mass%, the via resolution tends to be good.

< elastomer (D) >

The photosensitive resin composition of the present embodiment may contain an elastomer as the component (D), and is preferably contained. By containing the component (D), there is a tendency that the photosensitive resin composition is excellent in the resolution of through holes, the adhesion strength with copper plating, and the reliability of electrical insulation. Further, the component (D) also has the following effects: the reduction of flexibility and adhesion strength with copper plating due to internal deformation (internal stress) of the cured product caused by curing shrinkage of the component (A) is suppressed.

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

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

Examples of the elastomer include: styrene elastomer, olefin elastomer, polyester elastomer, urethane elastomer, polyamide elastomer, acrylic elastomer, silicone elastomer, etc., preferably at least 1 selected from them. These elastomers are composed of a hard segment component which tends to contribute to heat resistance and strength, and a soft segment component which tends to contribute to flexibility and toughness.

In the above examples, the component (D) preferably contains at least 1 selected from the group consisting of olefin-based elastomers, polyester-based elastomers and urethane-based elastomers, and more preferably contains a polyester-based elastomer, from the viewpoints of compatibility, solubility and adhesion strength with copper plating. The component (D) is more preferably at least 1 selected from the group consisting of olefin elastomers, polyester elastomers and urethane elastomers, and particularly preferably a polyester elastomer.

(styrene elastomer)

Examples of the styrene elastomer include: styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-ethylene-propylene-styrene block copolymers, and the like. The styrene elastomer may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the components constituting the styrene-based elastomer include: styrene; styrene derivatives such as α -methylstyrene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene.

The styrene elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 3,000 to 20,000.

In the present specification, the number average molecular weight is a value obtained by a Gel Permeation Chromatography (GPC) method using tetrahydrofuran as a solvent and converted into standard polystyrene.

As the styrene-based elastomer, commercially available products can be used, and as the commercially available products, there can be mentioned: tufprene, Solprene T, Asaprene T, and Tuftec (the above are manufactured by asahi chemicals corporation, "Tufprene", "Asaprene", and "Tuftec" are registered trademarks); elastomer AR (manufactured by Aron chemical industries, ltd.); kraton G, Califlex (manufactured by Shell Japan K.K.; JSR-TR, TSR-SIS, DYNARON (manufactured by JSR Co., Ltd.; DENKASTR (manufactured by DENKA K.K.); Quintac (manufactured by Nippon Rikusho K.K.); Quintac (registered trademark); TPE-SB series (manufactured by Sumitomo chemical Co., Ltd.); Rabalon (registered trademark); Rabalon (manufactured by Mitsubishi chemical Co., Ltd.); SEPTON, HYBRAR (registered trademark); Sumiflex (manufactured by Sumitomo Corp., Ltd.); LEOSTOMER, ACTER (manufactured by Riken Technis Co., Ltd.); and the like).

(olefin elastomer)

The olefin elastomer is a polymer or copolymer of an alpha-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 4-methylpentene, or the like. The olefin elastomer may have a hydroxyl group at a molecular terminal, and preferably has a hydroxyl group at a molecular terminal. The olefin elastomer can be used alone in 1 kind, can also be combined with more than 2 kinds.

Examples of the olefinic elastomer include: polyethylene, polybutadiene, hydroxyl-containing polyisopropylene, ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), and the like. Further, copolymers of the above-mentioned α -olefin having 2 to 20 carbon atoms and a non-conjugated diene having 2 to 20 carbon atoms such as dicyclopentadiene, 1, 4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, isoprene and the like can be exemplified. Further, carboxyl-modified NBR obtained by copolymerizing methacrylic acid and a butadiene-acrylonitrile copolymer is also included.

The olefin elastomer preferably has a number average molecular weight of 1,000 to 5,000, more preferably 1,500 to 3,500.

The olefin-based elastomer may be a commercially available product, and examples of the commercially available product include: MILASTOMER (trade name, manufactured by Mitsui chemical Co., Ltd.); EXACT (trade name, product of exxonmobil corporation); ENGAGE (trade name, manufactured by Takara Chemicals Co., Ltd.); poly ip, Poly bd (trade name, Kashin Co., Ltd.); hydrogenated styrene-butadiene rubber "DYNATON HSBR" (manufactured by JSR Corp., trade name); butadiene-acrylonitrile copolymer "NBR series" (product name, manufactured by JSR corporation); "XER series" (product name, manufactured by JSR Corp.) of butadiene-acrylonitrile copolymer modified with carboxyl groups at both ends; BF-1000 (trade name, manufactured by Nippon Caoda corporation) of epoxidized polybutadiene obtained by partially epoxidizing polybutadiene; PB-4700, PB-3600 (trade name: product name, manufactured by Daiishi Co., Ltd.).

(polyester elastomer)

Examples of the polyester elastomer include those 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; an aromatic diol represented by the following general formula (D-1). The diol compounds may be used alone in 1 kind, or in combination of 2 or more kinds.

[ solution 9]

(in the general formula (D-1), X^D1Is an alkylene group having 1 to 10 carbon atoms, an alkylidene group having 2 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, -SO₂-。R^D1And R^D2Each independently represents a halogen atom or an alkyl group having 1 to 12 carbon atoms. p and q are each independently an integer of 0 to 4, and r is 0 or 1. )

In the general formula (D-1), as X^D1Examples of the alkylene group having 1 to 10 carbon atoms include: methylene, 1, 2-dimethylene, 1, 3-trimethylene, 1, 4-tetramethylene, 1, 5-pentamethylene, and the like. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, and more preferably a methylene group, from the viewpoint of via resolution, adhesion strength to copper plating, and electrical insulation reliability.

As X^D1Examples of the alkylidene group having 2 to 10 carbon atoms include: ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, pentylidene, isoamylidene, and the like. The alkylidene group is preferably isopropylidene from the viewpoints of via resolution, adhesion strength to copper plating, and electrical insulation reliability.

As X^D1Examples of the cycloalkylene group having 4 to 8 carbon atoms include: cyclopentylene, cyclohexylene, cyclooctylene, and the like.

As X^D1Among the above, an alkylene group having 1 to 10 carbon atoms and an alkylidene group having 2 to 10 carbon atoms are preferable, and a methylene group and an isopropylidene group are more preferable.

In the general formula (D-1), as R^D1And R^D2Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As R^D1And R^D2Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and n-pentyl groups. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and still more preferably a methyl group.

p and q are each independently an integer of 0 to 4, preferably 0 or 1.

r is 0 or 1, either, and when r is 0, the structure represented by the following general formula (D-1') is obtained.

[ solution 10]

(in the general formula (D-1'), X^D1、R^D1And p are the same as in the general formula (D-1), and the preferable mode is also the same. )

Examples of the aromatic diol represented by the general formula (D-1) include bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane, and resorcinol.

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 polyester elastomer preferably has a number average molecular weight of 900 to 30,000, more preferably 1,000 to 25,000, and still more preferably 5,000 to 20,000.

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

(urethane elastomer)

As the urethane elastomer, for example, an elastomer containing a hard segment composed of a short-chain diol and a diisocyanate and a soft segment composed of a high-molecular (long-chain) diol and a diisocyanate can be suitably cited. The urethane elastomer may be used alone in 1 kind, or may be used in combination with 2 or more kinds.

Examples of the high-molecular (long-chain) diol include: polypropylene glycol, polytetrahydrofuran, poly (1, 4-butylene adipate), poly (1, 4-butylene ethylene-adipate), polycaprolactone, poly (1, 6-hexanediol carbonate), poly (1, 6-ethylene glycol-neopentyl glycol adipate), and the like. The number average molecular weight of the high-molecular (long-chain) diol is preferably 500 to 10,000.

Examples of the short-chain diol include ethylene glycol, propylene glycol, 1, 4-butanediol, and bisphenol a. The number average molecular weight of the short-chain diol is preferably 48 to 500.

The urethane elastomer preferably has a number average molecular weight of 1,000 to 25,000, more preferably 1,500 to 20,000, and still more preferably 2,000 to 15,000.

As the urethane elastomer, commercially available products can be used, and examples thereof include: NIPPOLAN 3116 (manufactured by Tosoh corporation, "NIPPOLAN" is a registered trademark), PANDEX T-2185, T-2983N (manufactured by DIC Co., Ltd.), MIRACTRAN series (manufactured by Japanese MIRACTRAN, "MIRACTRAN" is a registered trademark), Hitaloid series (manufactured by Hitaloid corporation, "Hitaloid" is a registered trademark), and the like.

(Polyamide elastomer)

Polyamide-based elastomers can be broadly classified into two types: polyether block amide type obtained by using polyamide in the hard segment and polyether in the soft segment; a polyether ester block amide type obtained by using a polyamide in the hard segment and a polyester in the soft segment.

Specific examples of the polyamide-based elastomer include: block copolymers in which polyamide is used as a hard block component and polybutadiene, butadiene-acrylonitrile copolymer, styrene-butadiene copolymer, polyisoprene, ethylene-propylene copolymer, polyether, polyester, polybutadiene, polycarbonate, polyacrylate, polymethacrylate, polyurethane, silicone rubber, or the like is used as a soft block component. The polyamide-based elastomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The polyamide elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000.

As the polyamide-based elastomer, commercially available products can be used, and examples thereof include: UBE polyamide elastomer (of Yu Xing corporation), DAIAMID (of Daiio Won Co., Ltd., "DAIAMID" is a registered trademark), PEBAX (of Toyoli corporation), Grilon ELY (of EMS-Chemie Japan Co., Ltd., "Grilon" is a registered trademark), Novamid (of Mitsubishi chemical corporation), Grelax (of Toyobo Co., Ltd., "Grelax" is a registered trademark), and the like.

(acrylic elastomer)

Examples of the acrylic elastomer include polymers of raw material monomers containing acrylic acid esters as a main component. The acrylic acid ester includes ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, and the like. The crosslinking monomer may be a monomer obtained by copolymerizing glycidyl methacrylate, allyl glycidyl ether, or the like, or may be a monomer obtained by copolymerizing acrylonitrile, ethylene, or the like. Specifically, there may be mentioned: acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like. The acrylic elastomer may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The acrylic elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000.

(Silicone elastomer)

The silicone elastomer is an elastomer containing an organopolysiloxane as a main component, and is classified into, for example, a polydimethylsiloxane elastomer, a polymethylphenylsiloxane elastomer, and a polydiphenylsiloxane elastomer. The organosilicon system may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The silicone elastomer preferably has a number average molecular weight of 1,000 to 50,000, more preferably 2,000 to 30,000.

As the silicone elastomer, commercially available products can be used, and examples thereof include: KE series (manufactured by shin & shin-Etsu chemical Co., Ltd.), SE series, CY series, and SH series (manufactured by Toyo Corning Ltd.).

(other Elastomers)

The component (D) may contain at least 1 selected from the group consisting of polyphenylene ether resins, phenoxy resins, polycarbonate resins, polyamideimide resins, polyimide resins, xylene resins, polyphenylene sulfide resins, polyetherimide resins, polyether ether ketone resins, tetrafluoroethylene resins, polyacrylonitrile resins, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene, and carboxyl-modified polyacrylonitrile.

(content of component (D))

When the photosensitive resin composition of the present embodiment contains the component (D), the content thereof is preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 15% by mass, particularly preferably 1 to 10% by mass, and most preferably 1 to 6% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (D) is 0.5% by mass or more, the effect of improving the adhesion strength with copper plating becomes sufficient, and the electrical insulation reliability tends to be further excellent. If the content of the component (D) is 20% by mass or less, the resolution of the through-hole, the adhesion strength to the copper plating, and the reliability of electrical insulation tend to be sufficient.

< E thermal polymerization initiator >

The photosensitive resin composition of the present embodiment may contain a thermal polymerization initiator as the component (E).

The thermal polymerization initiator is not particularly limited, and examples thereof include: hydroperoxides such as diisopropylbenzene hydroperoxide "PERCUYL P" (trade name, manufactured by Nichio oil Co., Ltd. (the same shall apply hereinafter)), cumene hydroperoxide "PERCUYL H", and tert-butyl hydroperoxide "PERBUTYL H"; dialkyl peroxides such as α, α -bis (t-butylperoxy-m-isopropyl) benzene "PERBUTYL P", dicumyl peroxide "PERCUTYL D", 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane "PERHEXA 25B", t-butylcumyl peroxide "PERBUTYL C", di-t-butyl peroxide "PERBUTYL D", 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexene-3 "PERHEXENE 25B", t-butyl peroxy-2-ethylhexanoate "PERBUTYL O"; ketone peroxides; peroxyketals such as n-butyl 4, 4-di (t-butylperoxy) valerate "PERHEXA V"; diacyl peroxides; peroxydicarbonates; organic peroxides such as peroxyesters; azo compounds such as 2,2 ' -azobisisobutyronitrile, 2 ' -azobis (2-cyclopropylpropionitrile) and 2,2 ' -azobis (2, 4-dimethylvaleronitrile). Among them, from the viewpoint of not impairing the photopolymerization property and having a large effect of improving the physical properties and characteristics of the photosensitive resin composition, a dialkyl peroxide is preferable, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexene-3 is more preferable.

The thermal polymerization initiator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(content of component (E))

When the photosensitive resin composition of the present embodiment contains the component (E), the content thereof is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and still more preferably 0.03 to 2% by mass, based on the total amount of the resin components of the photosensitive resin composition. If the content is 0.01% by mass or more, sufficient heat curing tends to be possible, and if the content is 5% by mass or less, the photosensitive properties and heat resistance tend to be good.

< inorganic Filler >

The photosensitive resin composition of the present embodiment may contain an inorganic filler as the component (F), and preferably contains an inorganic filler. By containing the inorganic filler, low thermal expansion can be achieved, and the possibility of occurrence of warpage is reduced. Although thermosetting resin compositions conventionally used as interlayer insulating layers of multilayer printed wiring boards have been reduced in thermal expansion by containing inorganic fillers, if a photosensitive resin composition is made to contain an inorganic filler, the inorganic filler causes light scattering and inhibits development, and thus it is difficult to reduce thermal expansion by containing a large amount of the inorganic filler. As described above, although there is a new problem in the photosensitive resin composition for the mode of containing an inorganic filler, the photosensitive resin composition of the present embodiment tends to have a high resolution of through holes even if it contains a large amount of an inorganic filler. Therefore, if the photosensitive resin composition of the present embodiment is used, both low thermal expansion and high resolution of the through hole can be achieved.

Examples of the component (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) Pansy (2 MgO. multidot.2Al)₂O₃·5SiO₂) Talc (3 MgO.4SiO)₂·H₂O), aluminum Titanate (TiO)₂·Al₂O₃) Yttrium-containing zirconium oxide (Y)₂O₃·ZrO₂) Silicic acid, silicic acidBarium (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 (calcined kaolin), carbon, and the like. (F) The components can be used alone in 1 kind, or can be used in combination in more than 2 kinds.

The average particle diameter of the component (F) is preferably 0.01 to 5 μm, more preferably 0.1 to 3 μm, still more preferably 0.1 to 2 μm, and particularly preferably 0.1 to 1 μm, from the viewpoint of the resolution of the through-hole. Here, the average particle diameter of the component (F) 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 component (F) contained in the photosensitive resin film and the interlayer insulating film provided on the carrier film may be measured by the above-mentioned submicron particle analyzer after being diluted (or dissolved) with a solvent to 1,000 times (volume ratio) as described above.

The component (F) preferably contains silica, and more preferably silica, from the viewpoint of heat resistance and low thermal expansion. In addition, the component (F) may be alumina or a surface-treated product of an organic silane compound, from the viewpoint of improving dispersibility of the inorganic filler in the photosensitive resin composition by the aggregation preventing effect.

(content of component (F))

When the photosensitive resin composition of the present embodiment contains the component (F), the content thereof is not particularly limited, but is preferably 5 to 80% by mass, more preferably 15 to 60% by mass, further preferably 25 to 55% by mass, and particularly preferably 30 to 50% by mass, based on the total solid content of the photosensitive resin composition. If the content of the component (F) is within the above range, the mechanical strength, heat resistance, via hole resolution, and the like can be improved.

< (G) pigment

The photosensitive resin composition of the present embodiment may contain a pigment as the (G) component according to a desired color for adjusting the photosensitivity and the like. The component (G) may be used by appropriately selecting a colorant which emits a desired color, and preferred colorants include known colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, and naphthalene black.

(content of component (G))

When the photosensitive resin composition of the present embodiment contains the component (G), the content thereof is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and still more preferably 0.05 to 2% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of sensitivity adjustment and the like.

< curing agent (H) >

The photosensitive resin composition of the present embodiment may contain a curing agent in order to further improve various properties such as heat resistance, adhesion strength to copper plating, and chemical resistance. In particular, when the thermosetting resin (C) contains an epoxy resin, an epoxy resin curing agent is preferably contained as the curing agent.

Examples of the component (H) include: imidazole derivatives such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole and 2-phenyl-4-methyl-5-hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-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; tertiary amines such as trimethylamine, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4, 6-tris (dimethylaminophenol), tetramethylguanidine, and m-aminophenol; polyvinyl phenol, polyvinyl phenol bromide; polyphenols such as phenol novolac and alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, and tris-2-cyanoethylphosphine; phosphonium salts such as tri-n-butyl (2, 5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4, 6-triphenylthiopyrylium hexafluorophosphate, and the like.

Among them, polyamines are preferable, and melamine is more preferable, from the viewpoint of further improving various properties such as heat resistance, adhesion strength to copper plating, and chemical resistance.

When the photosensitive resin composition of the present embodiment contains the component (H), the content thereof is preferably 0.01 to 20% by mass, more preferably 0.02 to 10% by mass, and still more preferably 0.03 to 3% by mass, based on the total amount of the resin components of the photosensitive resin composition.

< diluent >

In the photosensitive resin composition of the present embodiment, a diluent may be used as necessary. As the diluent, for example, an organic solvent or the like can be used. Examples of the organic solvent include: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 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 in the photosensitive resin composition is preferably 40 to 90% by mass, more preferably 50 to 80% by mass, and still more preferably 55 to 65% by mass. By adjusting the amount of the diluent in this manner, the applicability of the photosensitive resin composition is improved, and a further high-definition pattern can be formed.

< other additives >

The photosensitive resin composition of the present embodiment may contain, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol; thickeners 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 can be obtained 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.

In the case of using the photosensitive resin film in the form of a film, for example, a photosensitive resin film described later can be used, and in this case, a photosensitive layer having a desired thickness can be formed by laminating the photosensitive resin film on a carrier film using a laminator or the like. 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 a photosensitive layer which will be an interlayer insulating layer later, and 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 further preferably 5 to 40 μm from the viewpoint of thinning of the multilayer printed wiring board.

The photosensitive resin film of the present embodiment can be formed into a photosensitive layer which is an interlayer insulating layer after applying the photosensitive resin composition of the present embodiment to a carrier film by using a known application device such as a die coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater, and drying the composition.

Examples of the carrier film include polyester films such as polyethylene terephthalate films and polybutylene terephthalate films; polyolefin films such as polypropylene films and polyethylene films. The thickness of the carrier film may be appropriately selected from the range of 5 to 100. mu.m, preferably 5 to 60 μm, and more preferably 15 to 45 μm.

In addition, the photosensitive resin film of the present embodiment may be provided with a protective film on a surface opposite to a surface contacting the carrier film among the surfaces of the photosensitive layer. As the protective film, for example, a polymer film such as polyethylene or polypropylene 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 may be dried by hot air or by a dryer using 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 multilayer printed wiring board.

The photosensitive resin film of the present embodiment is excellent in resolution of through holes, adhesion strength to copper plating, crack resistance, 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.

[ multilayer printed Wiring Board and method for producing the same ]

The present invention also provides a multilayer printed wiring board including an interlayer insulating layer formed using the photosensitive resin composition or the photosensitive resin film of the present embodiment. The multilayer printed wiring board of the present embodiment is not particularly limited in its production method as long as it has a step of forming an interlayer insulating layer using the photosensitive resin composition of the present embodiment, and can be easily produced by the following production method of a multilayer printed wiring board of the present embodiment, for example.

Hereinafter, a method for producing a multilayer printed wiring board using the photosensitive resin film (photosensitive resin film for an interlayer insulating layer) of the present embodiment will be described as an example of a preferred embodiment of a method for producing a multilayer printed wiring board, with reference to fig. 1 as appropriate.

The multilayer printed wiring board 100A can be manufactured by a manufacturing method including the following steps (1) to (4), for example.

The step (1) is a step of laminating the photosensitive resin film of the present embodiment on one side or both sides of a circuit board (hereinafter referred to as "laminating step (1)").

And a step (2) of exposing and developing the photosensitive resin film laminated in the step (1) to form an interlayer insulating layer having a through hole (hereinafter referred to as "optical through hole forming step (2)").

And a step (3) of roughening the through-hole and the interlayer insulating layer (hereinafter referred to as "roughening step (3)").

And a step (4) of forming a circuit pattern on the interlayer insulating layer (hereinafter referred to as "circuit pattern forming step (4)").

(laminating step (1))

The laminating step (1) is a step of: the photosensitive resin film (photosensitive resin film for interlayer insulating layer) of the present embodiment is laminated on one side or both sides of a circuit substrate (substrate 101 having circuit pattern 102) using a vacuum laminator. Examples of the vacuum laminator include: a vacuum applicator manufactured by Nichigo-Morton, a vacuum pressure type laminator manufactured by Nichigo corporation, a roll type dry coater manufactured by Hitachi, and a vacuum laminator manufactured by Hitachi chemical electronics.

When the protective film is provided on the photosensitive resin film, the protective film is peeled off or removed, and then the photosensitive resin film is pressure-bonded and laminated on a circuit board while being pressurized and heated so as to be in contact with the circuit board.

The lamination can be carried out, for example, after preheating the photosensitive resin film and the circuit board as required, under a reduced pressure of 70 to 130 ℃ in pressure bonding temperature, 0.1 to 1.0MPa in pressure bonding pressure, and 20mmHg (26.7hPa) or less in air pressure, but is not particularly limited to this condition. The lamination method may be a batch method or a continuous method using a roll.

Finally, the photosensitive resin film (hereinafter, referred to as a photosensitive layer) laminated on the circuit board is cooled to near room temperature to form the interlayer insulating layer 103. The carrier film may be peeled off at this point, or may be peeled off after exposure as described later.

(Photovia hole Forming step (2))

In the optical via forming step (2), at least a part of the photosensitive resin film laminated on the circuit board is exposed to light and then developed. By exposure, the portion irradiated with the active light is photo-cured to form a pattern. The exposure method is not particularly limited, and for example, a method (mask exposure method) of irradiating an active Light beam in an image form through a negative or positive mask pattern called an original (art) may be used, or a method of irradiating an active Light beam in an image form by a Direct drawing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method may be used.

As the light source of the active light, a known light source can be used. Specific examples of the light source include: gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, argon lasers and the like; solid-state lasers such as YAG lasers; a light source that efficiently emits ultraviolet rays or visible rays, such as a semiconductor laser. The exposure amount is suitably selected depending on the light source used, the thickness of the photosensitive layer, etc., and when the photosensitive layer is 1 to 100 μm thick, for example, when ultraviolet light from a high-pressure mercury lamp is irradiated, the exposure amount is preferably 10 to 1,000mJ/cm²More preferably 15 to 500mJ/cm²。

In the development, the uncured portion of the photosensitive layer is removed from the substrate, whereby an interlayer insulating layer composed of a cured product cured by light curing is formed on the substrate.

When the carrier film is present on the photosensitive layer, the unexposed portion is removed (developed) after the removal of the carrier film. The development method includes wet development and dry development, and any of them can be used, but wet development is widely used, and wet development can be used in this embodiment.

In the wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of the developing method include a dipping method, a suspension immersion method, a spraying method, a method using brush coating, beating, blade coating, and shaking dipping. Among them, from the viewpoint of improving the resolution, the spray method is preferable, and among the spray methods, the high-pressure spray method is more preferable. The development may be performed by 1 method, or 2 or more methods may be combined.

The composition of the developer can be appropriately selected according to the composition of the photosensitive resin composition. Examples thereof include an alkaline aqueous solution, an aqueous developer, and an organic solvent developer, and among them, an alkaline aqueous solution is preferable.

In the step (2) of forming the light passing hole, the exposure and development may be carried outIf necessary, the concentration is 200 to 10,000mJ/cm²Degree (preferably 500 to 5,000 mJ/cm)²) Post UV curing with an exposure amount and post heat curing at a temperature of about 60 to 250 deg.C (preferably 120 to 200 deg.C) to further cure the interlayer insulating layer, and preferably so.

By the above operation, an interlayer insulating layer having the via hole 104 can be formed. The shape of the through hole is not particularly limited, and for example, a quadrangle, an inverted trapezoid (upper side longer than lower side), and the like can be cited if the shape is described as a cross-sectional shape, and a circle, a quadrangle, and the like can be cited if the shape is described as a front side (direction in which the bottom of the through hole is visible). In this embodiment, the through hole can be formed in an inverted trapezoidal cross-sectional shape (upper side longer than lower side) by the through hole formation by photolithography, and in this case, the copper plating is preferable because the coverage of the through hole wall surface is high.

The size (diameter) of the through hole formed in this step may be 60 μm or less, and may be 40 μm or less or 30 μm or less, and the diameter can be reduced as compared with the size of the through hole formed by laser processing. The lower limit of the size (diameter) of the through-hole formed in this step is not particularly limited, and may be 15 μm or more, or 20 μm or more.

The size (diameter) of the through hole formed in this step is not necessarily limited to 60 μm or less, and may be about 200 μm or less, for example, and may be arbitrarily selected from the range of 15 to 300 μm.

(roughening treatment step (3))

In the roughening treatment step (3), the surfaces of the via hole and the interlayer insulating layer are roughened by the roughening solution. When the smear is generated in the through-hole forming step (2), the smear can be removed by the roughening liquid. The roughening treatment and the removal of the smear can be performed simultaneously.

The roughening liquid includes: a chromium/sulfuric acid roughening solution, an alkaline permanganate roughening solution (for example, a sodium permanganate roughening solution), a sodium fluoride/chromium/sulfuric acid roughening solution, and the like.

By the roughening treatment, anchor points (anchors) having irregularities are formed on the surfaces of the via hole and the interlayer insulating layer.

(Circuit Pattern Forming step (4))

The circuit pattern forming step (4) is a step of forming a circuit pattern on the interlayer insulating layer after the roughening treatment step (3).

From the viewpoint of forming fine wiring, the formation of the circuit pattern is preferably performed by a semi-additive method. By the semi-additive method, the conduction of the via hole can be performed while forming the circuit pattern.

In the semi-additive method, first, electroless copper plating treatment is performed using a palladium catalyst or the like on the via bottom, the via wall surface, and the entire surface of the interlayer insulating layer after the roughening treatment step (3) to form the seed layer 105. The seed crystal layer is used for forming a power supply layer by electroplating copper, and is preferably formed to a thickness of about 0.1 to 2.0 μm. If the thickness of the seed crystal layer is 0.1 μm or more, there is a tendency that the reduction of the connection reliability at the time of copper plating can be suppressed, and if it is 2.0 μm or less, there is a tendency that the etching amount does not need to be increased at the time of flash etching (flash etching) of the seed crystal layer between the wirings, and the damage to the wirings at the time of etching can be suppressed.

The electroless copper plating treatment is performed by depositing metallic copper on the surfaces of the via hole and the interlayer insulating layer by a reaction between copper ions and a reducing agent.

The electroless plating method and the plating method may be any known methods, and are not particularly limited, and the catalyst in the electroless plating step is preferably a palladium-tin mixed catalyst, and the primary particle diameter of the catalyst is preferably 10nm or less. In addition, hypophosphorous acid is preferably contained as a reducing agent as a plating composition in the electroless plating step.

As the electroless copper plating solution, commercially available products can be used, and examples thereof include "MSK-DK" manufactured by Atotech Japan, and "THRU-CUP (registered trademark PEA ver.4)" manufactured by Shanmura industries, Ltd.

After the electroless copper plating treatment, the dry film resist was thermally pressed against the electroless copper plating by a roll laminator. The thickness of the dry film resist is preferably 5 to 30 μm in view of the necessity of being higher than the wiring height after copper electroplating. As the dry film resist, a "PHOTOC" series manufactured by Hitachi chemical Co., Ltd., or the like can be used.

After thermocompression bonding of the dry film resist, exposure of the dry film resist is performed, for example, through a mask on which a desired wiring pattern is drawn. The exposure can be performed using the same apparatus and light source that can be used when forming the through hole in the photosensitive resin film. After exposure, the carrier film on the dry film resist is peeled off, and the unexposed portion is removed by development with an alkaline aqueous solution, thereby forming a resist pattern 106. After that, an operation of removing the development residue of the dry film resist may be performed using plasma or the like as necessary.

After development, electrolytic copper plating is performed, thereby performing formation of the copper circuit layer 107 and via filling (via filling).

After the copper electroplating, the dry film resist is stripped using an alkaline aqueous solution or an amine stripper. After the dry film resist was peeled off, the seed layer between the wirings was removed (flash etching). The flash etching is performed using an acidic solution such as sulfuric acid or hydrogen peroxide and an oxidizing solution. Specifically, SAC manufactured by JCU, CPE-800 manufactured by Mitsubishi gas chemical company, and the like can be cited. After the flash etching, palladium or the like attached to the inter-wiring portion is removed as necessary. The removal of palladium can be preferably performed using an acidic solution such as nitric acid or hydrochloric acid.

After the dry film resist is peeled off or after the flash etching step, a post-baking treatment is preferably performed. The post-baking treatment makes the unreacted thermosetting component thermally cured sufficiently, thereby further improving the electrical insulation reliability, curing characteristics and adhesion strength with the copper plating. The heat curing conditions vary depending on the kind of the resin composition, and the curing temperature is preferably 150 to 240 ℃ and the curing time is preferably 15 to 100 minutes. The entire process of manufacturing the printed wiring board using the optical via method can be completed by the post-baking treatment, and the substrate can be manufactured by repeating this process depending on the number of interlayer insulating layers required. Also, the solder resist layer 108 is preferably formed on the outermost layer.

The method for producing a multilayer printed wiring board in which a through hole is formed using the photosensitive resin composition of the present embodiment has been described above, but the photosensitive resin composition of the present embodiment is excellent in pattern resolution, and therefore, is also suitable for forming a cavity for incorporating a chip, a passive element, or the like, for example. The cavity can be suitably formed by, for example, forming a drawing pattern when the photosensitive resin film is exposed to light and patterned in the above description of the multilayer printed wiring board as a pattern capable of forming a desired cavity.

Further, the photosensitive resin composition of the present embodiment is also useful as a surface protective film such as a solder resist layer.

[ semiconductor Package ]

The present invention also provides a semiconductor package in which the multilayer printed wiring board of the present embodiment is mounted with a semiconductor element. 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 multilayer 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 examples 1 to 3 and comparative examples 1 to 2 were evaluated for their properties by the following methods.

[1. evaluation of through-hole resolution ]

(1-1) production of laminate for evaluation

A copper foil surface of a substrate for a printed wiring board (product name "MCL-E-679" manufactured by hitachi chemical) obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy base material was treated with a roughening pretreatment liquid (product name "CZ-8100" manufactured by MEC corporation), and then washed with water and dried, thereby obtaining a substrate for a printed wiring board subjected to roughening pretreatment. Next, the protective film was peeled off from the photosensitive resin film with the carrier film and the protective film produced in each of examples and comparative examples, and the exposed photosensitive resin film was placed in contact with the copper foil of the substrate for a printed wiring board subjected to the roughening treatment, followed by lamination treatment using a pressure vacuum laminator (manufactured by nipples corporation, trade name "MVLP-500"). The lamination conditions were as follows: the temperature of the pressure heating plate is 70 ℃, the vacuumizing time is 20 seconds, the laminating and pressurizing time is 30 seconds, the air pressure is less than or equal to 4kPa, and the compression joint pressure is 0.4 MPa. After the lamination treatment, the laminate was left at room temperature for 1 hour or more, thereby obtaining a laminate for evaluation in which a photosensitive resin film and a carrier film were sequentially laminated on the copper foil surface of the substrate for a printed wiring board.

(1-2) measurement of sensitivity of photosensitive resin film

After the carrier film of the laminate for evaluation obtained above was peeled off and removed, a 41-stage exposure meter was arranged, and exposure was performed using a direct imaging exposure apparatus "DXP-3512" (manufactured by ORC corporation) using an ultra-high pressure mercury lamp as a light source. The exposure pattern used was a pattern in which dots were arranged in a lattice pattern (dot diameter: distance between dot centers: 1: 2). With respect to the diameter of the spot, inIn such a range that the diameter is changed by 5 μm at a time.

After exposure, the photosensitive resin composition was left at room temperature for 30 minutes, and then spray-developed for 60 seconds in the unexposed area using a1 mass% aqueous solution of sodium carbonate at 30 ℃. After the development, the exposure energy at which the number of the gloss remaining steps of the 41-step exposure table was 8.0 was set as the sensitivity (unit: mJ/cm) of the photosensitive resin film²). Using the pattern exposed with this sensitivity, the resolution of the through hole provided in the photosensitive resin film was evaluated according to the following evaluation criteria.

(1-3) evaluation of resolution

The resolution was evaluated by exposing the photosensitive resin film measured in (1-2) above with exposure energy at which the sensitivity, i.e., the number of steps, became 8.0, followed by spray development, and then observing the via hole pattern with an optical microscope according to the following criteria. The state of the "opening" described above means: when the through-hole portion of the dot pattern was observed using an optical microscope, the state of the copper foil of the base material for a printed wiring board was confirmed. The judgment of "A" indicates good characteristics.

A: dot pattern ofThe through-hole portion is opened.

B: dot pattern ofThe through-hole portion is not opened.

C: no photocuring was performed.

[2] evaluation of adhesion Strength (peeling Strength) to copper plating ]

The protective layer of the photosensitive film was peeled off, and the laminate was laminated on a copper-clad laminate substrate having a thickness of 1.0mm by using a pressure type vacuum laminator (product name "MVLP-500" manufactured by Kabushiki Kaisha) under conditions of a pressure bonding pressure of 0.4MPa, a pressure heating plate temperature of 80 ℃, an evacuation time of 25 seconds, a lamination pressure time of 25 seconds, and an air pressure of 4kPa or less, to obtain a laminate.

The obtained laminate was exposed to 500mJ/cm of light using a parallel light exposure machine (product name "EXM-1201" manufactured by ORC) using an ultra-high pressure mercury lamp as a light source²The whole surface is exposed. Next, an ultraviolet exposure apparatus was used at a dose of 2,000mJ/cm²The cured film was obtained on the copper-clad laminate by exposure to light and heating at 170 ℃ for 1 hour.

Next, in order to chemically roughen the surface of the cured product, an aqueous solution of 200ml/L diethylene glycol monobutyl ether and 5g/L sodium hydroxide was prepared as a swelling solution, and the swelling solution was heated to 70 ℃ and subjected to immersion treatment for 10 minutes. Next, an aqueous solution of 60g/L potassium permanganate and 40g/L sodium hydroxide was prepared as a roughening solution, and the solution was heated to 70 ℃ and subjected to immersion treatment for 15 minutes. Next, a neutralization solution (SnCl) was prepared₂) 30g/L of hydrogen chloride and 30g/L of hydrogen chloride0ml/L), heated to 40 ℃ and subjected to immersion treatment for 5 minutes, thereby reducing potassium permanganate.

Subsequently, the surface of the cured product after desmear treatment was treated with an alkaline cleaning solution (Cleaner securigant 902) at 60 ℃ for 5 minutes to perform degreasing and cleaning. After cleaning, the cured product after desmear treatment was treated with a prepreg (Pre-Dip Neogenath B) at 23 ℃ for 1 minute. Then, the cured product WAs treated with an activating solution (Activator Neogenh 834) at 35 ℃ for 5 minutes, and then, the cured product WAs treated with a reducing solution (Reducer Neogenh WA) at 30 ℃ for 5 minutes.

The laminate obtained in the above-described manner was put into a chemical copper solution (basic print ganth MSK-DK, copper print ganth MSK, or static print ganth MSK) and subjected to electroless plating until the plating thickness became about 0.5 μm. After the electroless plating, annealing was performed at a temperature of 120 ℃ for 30 minutes in order to remove residual hydrogen. Thereafter, copper sulfate plating was performed, and annealing treatment was performed at 180 ℃ for 60 minutes, thereby forming a conductor layer having a thickness of 25 μm.

The laminate having the conductor layer formed by the above-described procedure was evaluated by the following evaluation criteria, by measuring the vertical peel strength at 23 ℃ in accordance with JIS C6481 (1996).

A: the bonding strength with the copper plating is more than or equal to 0.40 kN/m.

B: the bonding strength with the copper plating is less than 0.40kN/m and more than or equal to 0.30 kN/m.

C: the bonding strength with the copper plating is less than 0.30 kN/m.

[3. evaluation of reliability of electric insulation (HAST resistance) ]

In the above [2] evaluation of adhesion strength (peel strength) to copper plating ], a laminate having a conductor layer formed thereon was obtained by performing the same operation except that a conductor layer having a thickness of 35 μm was formed instead of a conductor layer having a thickness of 25 μm.

The formed conductor layer is formed to beEtching is performed in the manner of a circular electrode. Then, applying pressureA laminate for evaluation was obtained by forming a photosensitive solder resist film "FZ-2700 GA" (trade name, manufactured by Hitachi chemical Co., Ltd.) on an electrode and a cured film under conditions of a pressure-bonding pressure of 0.4MPa, a pressure-heating plate temperature of 80 ℃, an evacuation time of 25 seconds, a lamination pressure time of 40 seconds, and an air pressure of 4kPa or less so that the thickness of the layer became 25 μm.

The laminate for evaluation obtained in the above-described manner was subjected to 500mJ/cm using a parallel light exposure machine (product name "EXM-1201" manufactured by ORC corporation) using an ultra-high pressure mercury lamp as a light source²The whole surface is exposed. Next, an ultraviolet exposure apparatus was used at a dose of 2,000mJ/cm²The exposure amount of (2) was used for exposure, and the resultant was heated at 160 ℃ for 1 hour to obtain a cured film.

Then, the wiring was formed so that the circular electrode was a positive electrode and the copper foil on the side of the copper-clad laminate substrate on which the circular electrode was formed was a negative electrode, and the wiring was exposed to a high-pressure cooker (model name "unsaturated type ultra accelerated life test equipment PC-422 RP", manufactured by heishan corporation) at 135 ℃, 85%, and 5.5V for 200 hours. The resistance value between the electrodes was measured and evaluated according to the following evaluation criteria.

A: resistance value of 10 x 10 or more after 200 hours⁷Ω。

B: resistance value of 10 x 10 or less after 200 hours⁷Omega is greater than or equal to 10 x 10⁶Ω。

C: the resistance value after 200 hours is less than 10 multiplied by 10⁶Ω。

< Synthesis example 1> Synthesis of acid-modified epoxy derivative 1 containing ethylenically unsaturated group and alicyclic skeleton [ (A1-1) component ]

350 parts by mass of a dicyclopentadiene type epoxy resin ("XD-1000" manufactured by Nippon chemical Co., Ltd., epoxy equivalent 252g/eq, softening point 74.2 ℃ C., corresponding to component (a1), represented by the above general formula (a1-1) having a ring-forming carbon number of an alicyclic skeleton of 10, 70 parts by mass of an acrylic acid (corresponding to component (a 2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were added, and the mixture was heated to 90 ℃ and stirred to react, thereby dissolving the mixture.

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. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a3) component) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ℃ and reacted for 6 hours.

Then, the reaction mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having a solid content of 73 mass% (corresponding to component (A1-1.) hereinafter referred to as "acid-modified epoxy derivative 1 containing an ethylenically unsaturated group and an alicyclic skeleton").

< Synthesis example 2> Synthesis of acid-modified epoxy derivative containing ethylenically unsaturated group and alicyclic skeleton 2[ (A1-1) component ]

350 parts by mass of a dicyclopentadiene type epoxy resin ("EPICLON (registered trademark) HP-7200" manufactured by DIC corporation, epoxy equivalent 254-264 g/eq, softening point 56-66 ℃, corresponding to component (a1), represented by the general formula (a1-1) above, having 10 ring-forming carbon atoms of the alicyclic skeleton, 70 parts by mass of acrylic acid (corresponding to component (a 2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were added, and the mixture was heated to 90 ℃ and stirred to react, thereby dissolving the mixture.

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. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a3) component) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ℃ and reacted for 6 hours.

Then, the reaction mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having a solid content of 74 mass% (corresponding to the component (A1-1), hereinafter referred to as "acid-modified epoxy derivative 2 containing an ethylenically unsaturated group and an alicyclic skeleton").

< Synthesis example 3> (A2-1) Synthesis of acid-modified ethylenically unsaturated group-containing epoxy derivative having no alicyclic skeleton

350 parts by mass of a bisphenol F novolak type epoxy resin ("EXA-7376" manufactured by DIC K.K., corresponding to the component (a 21)), 70 parts by mass of acrylic acid (corresponding to the component (a 22)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were added, and the mixture was reacted with stirring while heating to 90 ℃ to dissolve the mixture

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. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (corresponding to the (a23) component) and 85 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ℃ and reacted for 6 hours.

Then, the mixture was cooled to room temperature to obtain an acid-modified bisphenol F-type epoxy acrylate having a solid content of 73 mass% (corresponding to component (A2-1) hereinafter referred to as "acid-modified ethylenically unsaturated group-containing epoxy derivative 3").

< examples 1 to 3 and comparative examples 1 to 2>

(preparation of photosensitive resin composition)

The compositions were prepared in accordance with the formulation compositions and formulation amounts shown in table 1, and kneaded by a three-roll mill to prepare photosensitive resin compositions. In each example, carbitol acetate was added as appropriate to adjust the concentration, thereby obtaining a photosensitive resin composition having a solid content concentration of 60 mass%.

(production of photosensitive resin film)

A polyethylene terephthalate film (G2-25, manufactured by Kittman Co., Ltd., trade name) having a thickness of 25 μm was used as a carrier film, and on the carrier film, the photosensitive resin compositions prepared in each example were applied so that the film thickness after drying became 25 μm, and dried at 100 ℃ for 10 minutes using a hot air convection dryer, thereby forming a photosensitive resin film (photosensitive layer). Then, a biaxially stretched polypropylene film (MA-411, product name of Wangzi F-Tex) 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, to prepare a photosensitive resin film in which a carrier film and a 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 1.

[ Table 1]

TABLE 1

The amounts of the respective components to be blended are calculated as solid contents in the case of a solution.

The components used in each example are as follows.

(A) Ingredients;

acid-modified epoxy derivative 1 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ a1-1 ]: the substance obtained in synthesis example 1 was used.

Acid-modified epoxy derivative 2 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ a1-1 ]: the substance obtained in synthesis example 2 was used.

Acid-modified ethylenically unsaturated group-containing epoxy derivative 3[ (component a2-1 ]: the substance obtained in Synthesis example 3 was used.

Dipentaerythritol pentaacrylate [ (Aiii) component ]

(B) Ingredients;

photopolymerization initiator 1: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, acetophenones

Photopolymerization initiator 2: 2, 4-dimethylthioxanthones, thioxanthones

(C) Ingredients;

biphenyl type epoxy resin: "YX-4000" (product name manufactured by Mitsubishi chemical Co., Ltd.)

Epoxidized polybutadiene: "PB 3600" (product name of Daluo chemical Co., Ltd.)

(D) Ingredients;

polyester: "Espel (registered trademark) 1108" (trade name of Hitachi Kasei Co., Ltd.)

(F) Ingredients;

silica: "SFP-20M" (product name, average particle diameter 0.3 μ M, manufactured by DENKA K.K.)

As is clear from table 1, in examples 1 to 3, the results of excellent via hole resolution, adhesion strength with copper plating, and electrical insulation reliability were obtained. On the other hand, in comparative examples 1 and 2 containing no (a1) component, the adhesion strength with copper plating and the electrical insulation reliability were not sufficient.

Further, a photosensitive resin composition described later was separately prepared, and the resolution and the crack resistance were evaluated according to the following methods.

[4. evaluation of through-hole resolution ]

(4-1) production of laminate for evaluation

The copper foil surface of a printed wiring board substrate (product name "MCL-E-679" from Hitachi chemical Co., Ltd.) obtained by laminating a copper foil having a thickness of 12 μm on a glass epoxy substrate was polished with a polishing brush, washed with water and dried to obtain a substrate for a printed wiring board subjected to a roughening pretreatment. Next, the protective film was peeled off from the photosensitive resin film with the carrier film and the protective film prepared in each of examples and comparative examples, and the exposed photosensitive resin film was placed in contact with the copper foil of the substrate for a printed wiring board subjected to the roughening treatment, followed by lamination treatment using a pressure vacuum laminator (manufactured by ltd., product name, "MVLP-500"). The lamination conditions were as follows: the temperature of the pressure heating plate is 70 ℃, the vacuumizing time is 20 seconds, the laminating and pressurizing time is 20 seconds, the air pressure is less than or equal to 4kPa, and the compression joint pressure is 0.4 MPa. After the lamination treatment, the laminate was left at room temperature for 1 hour or more to obtain a laminate for evaluation, in which a photosensitive resin film and a carrier film were sequentially laminated on the surface of a copper foil of a substrate for a printed wiring board.

(4-2) sensitivity measurement of photosensitive resin film

After the carrier film of the laminate for evaluation obtained above was peeled off and removed, a 41-stage exposure meter was arranged, and exposure was performed using a direct imaging exposure apparatus "DXP-3512" (manufactured by ORC corporation) using an ultra-high pressure mercury lamp as a light source. As the exposure pattern, a pattern in which squares are arranged in a lattice shape (length of one side: distance between centers of squares: 1:2) was used.

After exposure, the substrate was left at room temperature for 30 minutes, and then the polyethylene terephthalate of the support was removed, and the photosensitive resin composition in the unexposed portion was subjected to spray development for 60 seconds using a1 mass% aqueous solution of sodium carbonate at 30 ℃. After the development, the exposure energy at which the number of the remaining gloss step stages on the 41-stage exposure chart was 10.0 was set as the sensitivity (unit: mJ/cm) of the photosensitive resin film²). Using the pattern exposed with this sensitivity, the resolution of the through hole provided in the photosensitive resin film was evaluated according to the following evaluation criteria.

(4-3) evaluation of resolution

The resolution was evaluated by exposing the photosensitive resin film measured in (4-2) above with exposure energy at which the sensitivity, i.e., the number of steps, became 10.0, followed by spray development, and then observing the via hole pattern with an optical microscope according to the following criteria. The "open" state mentioned above means: when the through-hole portion of the dot pattern was observed using an optical microscope, the state of the copper foil of the base material for a printed wiring board was confirmed. The judgment of "A" indicates good characteristics.

A: the bottom dimension of the via hole pattern having a side of 60 μm is 50 μm or more on one side.

B: the bottom dimension of the via hole pattern having a side of 60 μm is 40 μm or more and less than 50 μm on one side.

C: the bottom dimension of the via hole pattern having a side of 60 μm is 30 μm or more and less than 40 μm on one side.

[5. evaluation of crack resistance ]

The laminate for evaluation prepared in the same manner as in (4-1) above was exposed to an atmosphere at-65 ℃ for 15 minutes, then heated at a temperature rise rate of 180 ℃/minute, then exposed to an atmosphere at 150 ℃ for 15 minutes, and then cooled at a temperature rise rate of 180 ℃/minute, and the above thermal cycle was repeated 1,000 times.

Then, the degree of cracking and peeling of the laminate for evaluation at any 10 positions of the opening of the square through hole of 2mm square was observed by a metal microscope at a magnification of 100 times, and evaluated according to the following evaluation criteria.

A: no cracks and peeling were observed at all.

B: in 10, cracks and peeling were observed at 1 or 2.

C: in 10, cracks and peeling were observed in 3.

D: of 10, cracks and peeling were observed at 4 or more.

< Synthesis examples 4 to 5> Synthesis of acid-modified epoxy derivatives containing ethylenically unsaturated group and alicyclic skeleton 4 to 5[ (A1-1) component ]

350 parts by mass of a dicyclopentadiene type epoxy resin ("EPICLON (registered trademark) HP-7200" manufactured by DIC corporation, epoxy equivalent 254-264 g/eq, softening point 56-66 ℃, corresponding to component (a1), represented by the general formula (a1-1) above, having 10 ring-forming carbon atoms of the alicyclic skeleton, 70 parts by mass of acrylic acid (corresponding to component (a 2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were added, and the mixture was heated to 90 ℃ and stirred to react, thereby dissolving the mixture.

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. Tetrahydrophthalic anhydride (corresponding to component (a 3)) and carbitol acetate were added to the reacted solution, and the mixture was heated to 80 ℃ and reacted for 6 hours. The amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the acid-modified dicyclopentadiene type epoxy acrylate obtained was 60mgKOH/g or 80 mgKOH/g.

Then, the mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having an acid value of 60mgKOH/g in a solid content (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-and alicyclic skeleton-containing epoxy derivative 4"), and an acid-modified dicyclopentadiene type epoxy acrylate having an acid value of 80mgKOH/g in a solid content (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-and alicyclic skeleton-containing epoxy derivative 5").

< Synthesis examples 6 to 8> Synthesis of acid-modified epoxy derivatives containing ethylenically unsaturated group and alicyclic skeleton 6 to 8[ (A1-1) component ]

350 parts by mass of a dicyclopentadiene type epoxy resin ("XD-1000" manufactured by Nippon chemical Co., Ltd., epoxy equivalent 252g/eq, softening point 74.2 ℃ C., corresponding to component (a1), represented by the above general formula (a1-1) having a ring-forming carbon number of an alicyclic skeleton of 10, 70 parts by mass of an acrylic acid (corresponding to component (a 2)), 0.5 part by mass of methylhydroquinone, and 120 parts by mass of carbitol acetate were added, and the mixture was heated to 90 ℃ and stirred to react, thereby dissolving the mixture.

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. Tetrahydrophthalic anhydride (corresponding to the (a3) component) and carbitol acetate were added to the reacted solution, and the mixture was heated to 80 ℃ and reacted for about 6 hours. The amount of tetrahydrophthalic anhydride used was adjusted so that the acid value of the acid-modified dicyclopentadiene type epoxy acrylate obtained was 60mgKOH/g, 80mgKOH/g, or 100 mgKOH/g.

Then, the mixture was cooled to room temperature to obtain an acid-modified dicyclopentadiene type epoxy acrylate having a solid acid value of 60mgKOH/g (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-and alicyclic skeleton-containing epoxy derivative 6"), an acid-modified dicyclopentadiene type epoxy acrylate having a solid acid value of 80mgKOH/g (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-and alicyclic skeleton-containing epoxy derivative 7"), and an acid-modified dicyclopentadiene type epoxy acrylate having a solid acid value of 100mgKOH/g (corresponding to component (A1-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-and alicyclic skeleton-containing epoxy derivative 8").

< Synthesis example 9> Synthesis of acid-modified ethylenically unsaturated group-containing epoxy derivative having no alicyclic skeleton

682 parts by mass of an oxazolidone ring-containing epoxy resin, 104 parts by mass of acrylic acid, 0.5 part by mass of methylhydroquinone, 219 parts by mass of carbitol acetate were added, and the mixture was reacted by heating to 90 ℃ and stirring to dissolve the mixture.

Then, the obtained solution was cooled to 60 ℃,4 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. Tetrahydrophthalic anhydride and carbitol acetate were added to the solution after the reaction, and the mixture was heated to 80 ℃ to react for about 6 hours, and then cooled to obtain an acid-modified ethylenically unsaturated group-containing epoxy acrylate having a solid acid value of 80mgKOH/g (corresponding to component (A2-1), hereinafter referred to as "acid-modified ethylenically unsaturated group-containing epoxy derivative 9").

< examples 4 to 8 and comparative example 3>

(preparation of photosensitive resin composition)

The compositions were prepared according to the formulation compositions and formulation amounts shown in table 2, and kneaded by a three-roll mill to prepare photosensitive resin compositions. In each example, propylene glycol monomethyl ether acetate was added as appropriate to adjust the concentration, thereby obtaining a photosensitive resin composition having a solid content concentration of 50 mass%.

(production of photosensitive resin film)

The photosensitive resin compositions prepared in each example were applied to a polyethylene terephthalate film (G2-25, manufactured by Kittman Co., Ltd., trade name) having a thickness of 25 μm as a carrier film so that the film thickness after drying became 25 μm, and dried at 100 ℃ for 10 minutes using a hot air convection dryer to form a photosensitive resin film (photosensitive layer). Then, a biaxially stretched polypropylene film (MA-411, product name of Wangzi F-Tex) 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, to prepare a photosensitive resin film in which a carrier film and a 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 amounts of the respective components to be blended are calculated as solid contents in the case of a solution.

The components used in each example are as follows.

(A) Ingredients;

acid-modified epoxy derivative 4 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ a1-1 ]: the substance obtained in Synthesis example 4 was used.

Acid-modified epoxy derivative 5 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ A1-1 ]: the substance obtained in Synthesis example 5 was used.

Acid-modified epoxy derivative 6 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ A1-1 ]: the substance obtained in Synthesis example 6 was used.

Acid-modified epoxy derivative 7 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ A1-1 ]: the substance obtained in Synthesis example 7 was used.

Acid-modified epoxy derivative 8 containing an ethylenically unsaturated group and an alicyclic skeleton (component [ A1-1 ]: the substance obtained in Synthesis example 8 was used.

Acid-modified ethylenically unsaturated group-containing epoxy derivative 9[ (component a2-1 ]: the substance obtained in Synthesis example 9 was used.

Dipentaerythritol pentaacrylate [ (Aiii) component ]

(B) Ingredients;

photopolymerization initiator 1: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, acetophenones

Photopolymerization initiator 2: 2, 4-dimethylthioxanthones, thioxanthones

(C) Ingredients;

biphenyl type epoxy resin: "YX-4000" (product name manufactured by Mitsubishi chemical Co., Ltd.)

O-cresol novolac type epoxy resins: "EPICLON-680" (product name of DIC Co., Ltd.)

(F) Ingredients;

silica: "SFP-20M" (product name, average particle diameter 0.3 μ M, manufactured by DENKA K.K.)

(G) Ingredients;

pigment: pigment blue 15 (phthalocyanine pigment, Shanyang pigment Co., Ltd., trade name)

(H) Ingredients;

curing agent 1: finely divided melamine (product name of Nissan chemical industry Co., Ltd.)

Curing agent 2: 2-ethyl-4-methylimidazole

As is clear from Table 2, in examples 4 to 8, the results of excellent via hole resolution and crack resistance were obtained. On the other hand, in comparative example 3 containing no (a1) component, the via resolution and the crack resistance were not sufficient.

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.