Photosensitive resin film, printed wiring board, semiconductor package, and method for manufacturing printed wiring board

Abstract

The present invention relates to a photosensitive resin film which contains (A) a compound having an ethylenically-unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a fluorine-containing resin, wherein: the photosensitive resin film has a first surface, and a second surface opposite the first surface; the photosensitive resin film is irradiated with ultraviolet light at 2 J / cm2 and then heated for one hour at 170°C to achieve curing; thereafter, under conditions of a prescribed roughening treatment, a is less than b and a is 10 g / m2 or less when a is the amount of weight loss when the roughening treatment is carried out with the first surface exposed and the second surface unexposed, and b is the amount of weight loss when the roughening treatment is carried out with the second surface exposed and the first surface unexposed.

Description

[Technical Field]

[0001] The present disclosure relates to a photosensitive resin film, a printed wiring board, a semiconductor package, and a method for manufacturing a printed wiring board. [Background technology]

[0002] In recent years, electronic devices have become smaller and more powerful, and printed wiring boards are becoming increasingly dense due to an increase in the number of circuit layers and finer wiring. In particular, the density of semiconductor packages such as BGA (ball grid array) and CSP (chip size package) on which semiconductor chips are mounted has increased significantly. Therefore, in addition to finer wiring, printed wiring boards are required to have thinner interlayer insulating layers and smaller diameter vias for interlayer connection.

[0003] A conventional method for manufacturing a printed wiring board is a build-up method (see, for example, Patent Document 1) for forming a multilayer printed wiring board by sequentially laminating an interlayer insulating layer and a conductor circuit layer. As circuits become finer, the semi-additive method for forming circuits by plating has become mainstream for multilayer printed wiring boards. In conventional semi-additive methods, a thermosetting resin film has been used to form the interlayer insulating layer.

[0004] Laser processing is the mainstream method for forming vias in interlayer insulating layers formed from thermosetting resin films. However, the ability to reduce the diameter of vias using laser processing is reaching its limit. Furthermore, when forming vias using laser processing, each via hole must be formed individually. Therefore, when a large number of vias need to be formed to achieve high density, forming the vias takes a long time, resulting in high manufacturing costs and poor manufacturing efficiency.

[0005] Under these circumstances, a method has been proposed in which a plurality of small diameter vias are formed at once by photolithography using a photosensitive resin film (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 7-304931 [Patent Document 2] Japanese Patent Application Publication No. 2017-116652 Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, electronic devices have been using signals that are faster and larger in capacity. Accordingly, substrate materials for printed wiring boards are required to have dielectric properties (hereinafter sometimes referred to as "high-frequency properties") that can reduce transmission loss of high-frequency signals, i.e., low dielectric constant and low dielectric loss tangent.

[0008] The present inventors have investigated the incorporation of a fluorine-containing resin with a low dielectric constant into a photosensitive resin film for forming an interlayer insulating layer in order to improve the dielectric properties of the substrate material. However, simply incorporating a fluorine-containing resin into a photosensitive resin film has the problem that, although the dielectric constant of the interlayer insulating layer can be reduced, the adhesion of the conductor, particularly the adhesive strength to plated copper, is reduced. Therefore, it has been difficult to achieve both excellent dielectric properties and conductor adhesion.

[0009] In view of the current situation, the present embodiment aims to provide a photosensitive resin film capable of forming an interlayer insulating layer having excellent dielectric properties and conductor adhesion, a printed wiring board using the photosensitive resin film, a method for manufacturing the same, and a semiconductor package. [Means for solving the problem]

[0010] As a result of investigations into solving the above problems, the present inventors have found that the above problems can be solved by the present embodiment described below. That is, this embodiment relates to the following [1] to

[12] . [1] A photosensitive resin film containing (A) a compound having an ethylenically unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a fluorine-containing resin, the photosensitive resin film has a first surface and a second surface opposite to the first surface; 2 J / cm on the photosensitive resin film 2 After irradiating with ultraviolet light, it is cured by heating at 170°C for 1 hour, and then The weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the first surface is exposed and the second surface is not exposed is a, When the weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the second surface is exposed and the first surface is not exposed is defined as b, a is smaller than b and a is 10 g / m 2 The following is a photosensitive resin film. (Roughening treatment conditions) The object to be roughened is immersed in a swelling solution at 70°C for 5 minutes, then in an oxidizing agent solution at 80°C for 15 minutes, and further in a neutralizing solution at 50°C for 5 minutes, and then dried. [2] The photosensitive resin film according to the above [1], wherein the (A) compound having an ethylenically unsaturated group is a compound having an ethylenically unsaturated group and an acidic substituent. [3] The photosensitive resin film according to [1] or [2] above, wherein the (B) thermosetting resin is at least one selected from the group consisting of epoxy resins, maleimide resins, allyl resins, and vinyl resins. [4] The photosensitive resin film according to any one of the above [1] to [3], wherein the (D) inorganic filler contains silica, and the content of the silica is 2 to 60 mass %. [5] The (D) inorganic filler has a true density of 1,500 kg / m 3 The photosensitive resin film according to any one of the above [1] to [4], which contains the following silica: [6] The photosensitive resin film according to any one of the above [1] to [5], wherein the content of the (E) fluorine-containing resin is 5 to 60 mass % based on the total amount of resin components of the photosensitive resin film. [7] The photosensitive resin film according to any one of the above [1] to [6], further comprising (F) an elastomer. [8] The photosensitive resin film according to any one of the above [1] to [7], wherein the first surface is a surface on which a circuit pattern is formed by copper plating, and the second surface is an attachment surface when laminating the photosensitive resin film. [9] The photosensitive resin film according to any one of the above [1] to [8], which is used for forming an interlayer insulating layer having a photovia.

[10] A printed wiring board having an interlayer insulating layer which is a cured product of the photosensitive resin film according to any one of [1] to [9] above.

[11] A semiconductor package having the printed wiring board described in

[10] above.

[12] A method for manufacturing a printed wiring board, comprising the following steps (1) to (4): (1): The photosensitive resin film according to any one of the above [1] to [9] is laminated onto one or both sides of a circuit board in a state where the second surface serves as an attachment surface. (2) Forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in (1) above. (3): Heat-curing the interlayer insulating layer having the vias. (4) Forming a circuit pattern on the surface of the interlayer insulating layer opposite to the circuit board. [Effects of the Invention]

[0011] According to the present embodiment, it is possible to provide a photosensitive resin film capable of forming an interlayer insulating layer having excellent dielectric properties and conductor adhesion, a printed wiring board using the photosensitive resin film, a method for manufacturing the same, and a semiconductor package. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a schematic diagram showing one embodiment of a manufacturing process for a printed wiring board using the photosensitive resin film of the present embodiment as a material for an interlayer insulating layer. DETAILED DESCRIPTION OF THE INVENTION

[0013] In the numerical ranges described herein, the lower and upper limits of the numerical ranges may be replaced with values ​​shown in the examples. Furthermore, the lower and upper limits of the numerical ranges may be arbitrarily combined with the lower or upper limits of other numerical ranges. In the expression "AA to BB," the numerical values ​​AA and BB at the ends are included as the lower and upper limits, respectively, of the numerical range.

[0014] In this specification, for example, the expression "10 or more" means 10 or a numerical value exceeding 10, and this also applies when the numerical values ​​are different. Furthermore, for example, the expression "10 or less" means 10 or a numerical value less than 10, and this also applies when the numerical values ​​are different.

[0015] In this specification, when there are multiple substances corresponding to each component, the content of each component means the total content of the multiple substances, unless otherwise specified.

[0016] In this specification, "solid content" refers to non-volatile content excluding volatile substances such as solvents. In other words, "solid content" refers to components that remain without volatilization when the resin composition is dried, and includes liquid, starch syrup-like, and wax-like components at room temperature. Here, in this specification, room temperature refers to 25°C.

[0017] As used herein, the term "number of ring carbon atoms" refers to the number of carbon atoms necessary to form a ring, and does not include the number of carbon atoms of substituents on the ring. For example, both a cyclohexane skeleton and a methylcyclohexane skeleton have 6 ring carbon atoms.

[0018] The expression "(meth)acrylic XX" means either or both of acrylic XX and the corresponding methacrylic XX. Also, the expression "(meth)acryloyl group" means either or both of an acryloyl group and a methacryloyl group.

[0019] In this specification, when the term "layer" is used, for example, as in an interlayer insulating layer, the term "layer" includes not only a solid layer, but also a layer that is not a solid layer but has some islands, has holes, or has an unclear interface with an adjacent layer.

[0020] The mechanism of action described in this specification is speculation and does not limit the mechanism by which the effects of this embodiment are achieved.

[0021] Any combination of the features described in this specification is also included in this embodiment.

[0022] [Photosensitive resin film] The photosensitive resin film of this embodiment is A photosensitive resin film containing (A) a compound having an ethylenically unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a fluorine-containing resin, the photosensitive resin film has a first surface and a second surface opposite to the first surface; 2 J / cm on the photosensitive resin film 2 After irradiating with ultraviolet light, it is cured by heating at 170°C for 1 hour, and then The weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the first surface is exposed and the second surface is not exposed is a, When the weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the second surface is exposed and the first surface is not exposed is defined as b, a is smaller than b and a is 10 g / m 2 The following is a photosensitive resin film. (Roughening treatment conditions) The object to be roughened is immersed in a swelling solution at 70°C for 5 minutes, then in an oxidizing agent solution at 80°C for 15 minutes, and further in a neutralizing solution at 50°C for 5 minutes, and then dried.

[0023] In this specification, the components may be abbreviated as "component (A)," "component (B)," etc., as appropriate. In the following explanation, the photosensitive resin film is exposed to 2 J / cm 2 and then cured by heating at 170°C for 1 hour is referred to as a "cured film," and the weight loss a when roughening treatment is performed in a state where the first surface is exposed and the second surface is not exposed is sometimes referred to as "weight loss a of the first surface," and the weight loss b when roughening treatment is performed in a state where the second surface is exposed and the first surface is not exposed is sometimes referred to as "weight loss b of the second surface."

[0024] The photosensitive resin film of this embodiment can form a pattern such as a via by exposure and development. Therefore, the photosensitive resin film of this embodiment is suitable for forming an interlayer insulating layer having a photovia. In this specification, the term "photovia" refers to a via formed by photolithography, i.e., exposure and development.

[0025] The total thickness of the photosensitive resin film of this embodiment is not particularly limited, and may be, for example, 2 to 110 μm, 4 to 60 μm, or 7 to 50 μm.

[0026] <Weight loss after roughening treatment> In the photosensitive resin film of this embodiment, the weight loss a of the first surface is lower than the weight loss b of the second surface, so that the interlayer insulating layer obtained by curing the photosensitive resin film of this embodiment exhibits high adhesive strength with plated copper. The reason for this is presumed to be as follows: The fact that the weight loss amount a of the first surface is lower than the weight loss amount b of the second surface is thought to indicate that there is little resin elution from the first surface due to the roughening treatment. Therefore, even after the first surface was subjected to the roughening treatment step before forming the plated copper, there was a large amount of resin on the surface that contributes to adhesion with the plated copper, and as a result, this surface exhibited high adhesive strength with the plated copper. From the viewpoint of fully realizing this effect, it is preferable that the first surface of the photosensitive resin film of this embodiment is the surface on which a circuit pattern is formed by copper plating, and the second surface is the attachment surface when laminating the photosensitive resin film.

[0027] The weight loss amount a of the first surface is set to 10 g / m from the viewpoint of forming an interlayer insulating layer having superior dielectric properties and conductor adhesion. 2 or less, preferably 0.1 to 3.3 g / m 2 , more preferably 0.5 to 3.0 g / m 2 , and more preferably 0.8 to 2.7 g / m 2 is. The weight loss amount b of the second surface is not particularly limited as long as it is higher than the weight loss amount a of the first surface. However, from the viewpoint of forming an interlayer insulating layer having superior dielectric properties and conductor adhesion, it is preferably in the range higher than the weight loss amount a of the first surface, and is preferably 2.5 to 5.0 g / m 2 , more preferably 2.7 to 4.5 g / m 2 , and more preferably 3.0 to 4.0 g / m 2 is. The ratio [a / b] of the weight loss amount a on the first surface to the weight loss amount b on the second surface is less than 1 in mass ratio, preferably 0.05 to 0.95, more preferably 0.1 to 0.9, and even more preferably 0.2 to 0.8, from the viewpoint of forming an interlayer insulating layer having superior dielectric properties and conductor adhesion. The weight loss amounts a and b are measured by the method described above, and more specifically, can be measured by the method described in the Examples. The weight loss amount a of the first surface can be made lower than the weight loss amount b of the second surface, for example, by making the content of the (D) inorganic filler on the first surface side higher than that of the (D) inorganic filler on the second surface side in the photosensitive resin film of this embodiment, or by making the content of the (E) fluorine-containing resin on the first surface side lower than that of the (E) fluorine-containing resin on the second surface side.

[0028] In order to create a difference in the amount of weight loss between the first surface and the second surface, the photosensitive resin film of this embodiment is preferably produced using a resin composition for forming the first surface of the photosensitive resin film (hereinafter also referred to as "resin composition (1)") and a resin composition for forming the second surface (hereinafter also referred to as "resin composition (2)"). The resin composition (1) contains (A) a compound having an ethylenically unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, and (D) an inorganic filler, and preferably contains silica as the inorganic filler (D). The resin composition (2) preferably contains (A) a compound having an ethylenically unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a fluorine-containing resin. Below, each component contained in the photosensitive resin film of the present embodiment will be explained, and preferred embodiments of the resin composition (1) and the resin composition (2) will also be explained.

[0029] <(A) Compound Having an Ethylenically Unsaturated Group> The component (A) is not particularly limited as long as it is a compound having an ethylenically unsaturated group. The component (A) may be used alone or in combination of two or more types.

[0030] The component (A) is a compound that exhibits photopolymerizability, particularly radical polymerizability, due to the presence of an ethylenically unsaturated group. In this specification, the term "ethylenically unsaturated group" refers to a substituent containing an ethylenically unsaturated bond. The term "ethylenically unsaturated bond" refers to a carbon-carbon double bond capable of undergoing an addition reaction, and does not include double bonds in aromatic rings. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a (meth)acryloyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, etc. Among these, a (meth)acryloyl group is preferred from the viewpoint of reactivity.

[0031] The photosensitive resin film of this embodiment preferably contains (A1) a compound having an ethylenically unsaturated group and an acidic substituent from the viewpoint of enabling alkaline development, and preferably contains (A2) a monomer having two or more ethylenically unsaturated groups together with component (A1) from the viewpoint of forming an interlayer insulating layer having excellent heat resistance and dielectric properties. Components (A1) and (A2) are described below.

[0032] <(A1) Compound Having an Ethylenically Unsaturated Group and an Acidic Substituent> Examples of the acidic substituent contained in the component (A1) include a carboxy group, a sulfonic acid group, a phenolic hydroxyl group, etc. Of these, the carboxy group is preferred from the viewpoint of resolution. There are no particular limitations on the acid value of the component (A1), but it is preferably 20 to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g, and even more preferably 70 to 150 mgKOH / g. When the acid value of the component (A1) is at least as high as the above lower limit, the alkali developability tends to be better, and when the acid value of the component (A1) is at most the above upper limit, the relative dielectric constant tends to be better. The acid value of the component (A1) can be measured by the method described in the examples.

[0033] There are no particular limitations on the weight average molecular weight (Mw) of the component (A1), but it is preferably 600 to 30,000, more preferably 800 to 20,000, even more preferably 1,000 to 10,000, and particularly preferably 1,200 to 4,000. When the weight average molecular weight (Mw) of the component (A1) is within the above range, it tends to be possible to form an interlayer insulating layer that is superior in adhesive strength with plated copper, heat resistance, and insulation reliability. In this specification, the weight average molecular weight (Mw) is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted into standard polystyrene, and more specifically, is a value measured according to the method described in the Examples.

[0034] From the viewpoint of achieving a low dielectric constant and a low dielectric loss tangent, the component (A1) preferably contains an alicyclic skeleton. From the viewpoints of resolution and dielectric properties, the alicyclic skeleton of the component (A1) is preferably an alicyclic skeleton having 5 to 20 ring carbon atoms, more preferably an alicyclic skeleton having 5 to 18 ring carbon atoms, still more preferably an alicyclic skeleton having 6 to 16 ring carbon atoms, particularly preferably an alicyclic skeleton having 7 to 14 ring carbon atoms, and most preferably an alicyclic skeleton having 8 to 12 ring carbon atoms.

[0035] From the viewpoints of resolution and dielectric properties, the alicyclic skeleton of component (A1) preferably consists of two or more rings, more preferably two to four rings, and even more preferably three rings. Examples of alicyclic skeletons consisting of two or more rings include a norbornane skeleton, a decalin skeleton, a bicycloundecane skeleton, and a saturated dicyclopentadiene skeleton. Of these, from the viewpoints of resolution and dielectric properties, a saturated dicyclopentadiene skeleton is preferred. From the same viewpoint, the component (A1) preferably contains an alicyclic skeleton represented by the following general formula (A1-1).

[0036] [ka] (In the formula, R A1 represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. 1 is an integer from 0 to 6. * indicates a binding site.

[0037] In the above general formula (A1-1), R A1 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred.

[0038] In the above general formula (A1-1), m 1is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0. 1 is an integer between 2 and 6, multiple R A1 may be the same or different. A1 may be substituted on the same carbon atom or on different carbon atoms, to the extent possible.

[0039] In the above general formula (A1-1), * represents a bonding site to another structure. The single bond having the bonding site * may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to the carbon atom represented by either 1 or 2 and the carbon atom represented by either 3 or 4 in the following general formula (A1-1'):

[0040] [ka] (In the formula, R A1 , m 1 and * are the same as those in the general formula (A1-1) above.

[0041] The component (A1) is preferably a compound obtained by reacting (a1) an epoxy resin with (a2) a (meth)acryloyl group-containing organic acid, with (a3) ​​a saturated or unsaturated group-containing polybasic acid anhydride. In the following description, the compound obtained by reacting (a1) the epoxy resin with (a2) the (meth)acryloyl group-containing organic acid may be referred to as "component (A')." Furthermore, the compound obtained by reacting component (A') with (a3) ​​a saturated or unsaturated group-containing polybasic acid anhydride is sometimes referred to as an "acid-modified (meth)acryloyl group-containing epoxy resin derivative." Preferred embodiments of the component (A1) are described below.

[0042] ((a1) Epoxy resin) (a1) The epoxy resin preferably has two or more epoxy groups. The (a1) epoxy resin may be used alone or in combination of two or more kinds.

[0043] (a1) Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0044] (a1) Epoxy resins can be classified into various epoxy resins depending on the difference in the main skeleton, for example, epoxy resins having an alicyclic skeleton, novolac epoxy resins, bisphenol epoxy resins, aralkyl epoxy resins, other epoxy resins, etc. Among these, epoxy resins having an alicyclic skeleton and novolac epoxy resins are preferred.

[0045] [Epoxy resin having an alicyclic skeleton] The alicyclic skeleton of the epoxy resin having an alicyclic skeleton is explained in the same manner as the alicyclic skeleton of the component (A1) described above, and preferred embodiments are also the same. The epoxy resin having an alicyclic skeleton is preferably an epoxy resin represented by the following general formula (A1-2).

[0046] [ka] (In the formula, R A1 R each independently represents an alkyl group having 1 to 12 carbon atoms, and may be substituted anywhere in the alicyclic skeleton. A2 Each of m independently represents an alkyl group having 1 to 12 carbon atoms. 1 is an integer between 0 and 6, m 2 is an integer between 0 and 3. n is a number between 0 and 50.

[0047] In the above general formula (A1-2), R A1 represents R in the above general formula (A1-1). A1 The preferred embodiments are also the same. R in the above general formula (A1-2) A2 Examples of the alkyl group having 1 to 12 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. m in the above general formula (A1-2) 1 is m in the above general formula (A1-1). 1 The preferred embodiments are also the same. m in the above general formula (A1-2) 2 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0. In the general formula (A1-2), n represents the number of structural units in the parentheses and is a number from 0 to 50. Usually, epoxy resins are mixtures of resins with different numbers of structural units in the parentheses, and in such cases, n represents the average value of the mixture. Preferably, n is a number from 0 to 30.

[0048] As the epoxy resin having an alicyclic skeleton, commercially available products may be used, and examples of commercially available products include "ZXR-1807H" (trade name, manufactured by Nippon Kayaku Co., Ltd.), "XD-1000" (trade name, manufactured by Nippon Kayaku Co., Ltd.), and "EPICLON (registered trademark) HP-7200" (trade name, manufactured by DIC Corporation).

[0049] [Novolac-type epoxy resin] Examples of novolac epoxy resins include bisphenol novolac epoxy resins such as bisphenol A novolac epoxy resins, bisphenol F novolac epoxy resins, and bisphenol S novolac epoxy resins; phenol novolac epoxy resins, cresol novolac epoxy resins, biphenyl novolac epoxy resins, and naphthol novolac epoxy resins. The novolac type epoxy resin is preferably an epoxy resin having a structural unit represented by the following general formula (A1-3).

[0050] [ka] (In the formula, R A3 each independently represents a hydrogen atom or a methyl group; Y A1 Each of Y independently represents a hydrogen atom or a glycidyl group. A1 At least one of the groups is a glycidyl group.

[0051] R in the above general formula (A1-3) A3 From the viewpoint of resolution, it is preferable that Y in the above general formula (A1-3) are both hydrogen atoms. A1 are preferably all glycidyl groups.

[0052] The number of structural units in the epoxy resin (a1) having the structural unit represented by the general formula (A1-3) is 1 or more, preferably 10 to 100, more preferably 13 to 80, and even more preferably 15 to 70. When the number of structural units is within the above range, an interlayer insulating layer having better conductor adhesion, heat resistance, and insulation reliability tends to be formed.

[0053] As the epoxy resin having a structural unit represented by the general formula (A1-3), a commercially available product may be used. Examples of commercially available products include the "EXA-7376" series (trade name, manufactured by DIC Corporation, where R A3 are all hydrogen atoms, and Y A1 glycidyl groups), "EPON SU8" series (trade name, manufactured by Mitsubishi Chemical Corporation, in which R A3 are all methyl groups, and Y A1 and epoxy resins in which all of the groups are glycidyl groups.

[0054] [Bisphenol-type epoxy resin] Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and 3,3',5,5'-tetramethyl-4,4'-diglycidyloxydiphenylmethane.

[0055] [Aralkyl-type epoxy resin] Examples of aralkyl type epoxy resins include phenol aralkyl type epoxy resins, biphenyl aralkyl type epoxy resins, and naphthol aralkyl type epoxy resins.

[0056] [Other epoxy resins] Examples of other epoxy resins include stilbene-type epoxy resins, naphthalene-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, dihydroanthracene-type epoxy resins, cyclohexanedimethanol-type epoxy resins, trimethylol-type epoxy resins, alicyclic epoxy resins, aliphatic linear epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and rubber-modified epoxy resins.

[0057] ((a2) (Meth)acryloyl group-containing organic acid) (a2) The (meth)acryloyl group-containing organic acid is preferably a (meth)acryloyl group-containing monocarboxylic acid. Examples of (meth)acryloyl group-containing monocarboxylic acids include acrylic acid, acrylic acid dimers, methacrylic acid, acrylic acid derivatives such as β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid; half-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides; and half-ester compounds which are reaction products of (meth)acryloyl group-containing monoglycidyl ethers or (meth)acryloyl group-containing monoglycidyl esters and dibasic acid anhydrides. The component (a2) may be used alone or in combination of two or more.

[0058] In the reaction between component (a1) and component (a2), the amount of component (a2) used relative to 1 equivalent of epoxy groups in component (a1) is not particularly limited, but is preferably 0.6 to 1.1 equivalents, more preferably 0.8 to 1.05 equivalents, and even more preferably 0.9 to 1.02 equivalents. By reacting component (a1) and component (a2) in the above ratio, the polymerizability of component (A1) is improved, and resolution tends to be improved.

[0059] The components (a1) and (a2) are preferably dissolved in an organic solvent and reacted under heating. If necessary, known reaction catalysts, polymerization inhibitors, etc. may be used during the reaction.

[0060] When a (meth)acryloyl group-containing monocarboxylic acid is used as component (a2), component (A') obtained by reacting components (a1) and (a2) has hydroxyl groups formed by a ring-opening addition reaction between the epoxy groups of component (a1) and the carboxyl groups of component (a2). Next, component (A') is reacted with saturated or unsaturated group-containing polybasic acid anhydride (a3) ​​to obtain an acid-modified (meth)acryloyl group-containing epoxy resin derivative in which the hydroxyl groups of component (A') and the acid anhydride groups of component (a3) ​​are semi-esterified. The hydroxyl groups of component (A') may also include hydroxyl groups originally present in component (a1).

[0061] ((a3) Polybasic acid anhydride) The component (a3) ​​may contain a saturated group or an unsaturated group. Examples of the component (a3) ​​include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride. Among these, tetrahydrophthalic anhydride is preferred from the viewpoint of resolution. The component (a3) ​​may be used alone or in combination of two or more.

[0062] In the reaction between component (A') and component (a3), for example, the acid value of the acid-modified (meth)acryloyl group-containing epoxy resin derivative can be well adjusted by reacting 0.1 to 1.0 equivalents of component (a3) ​​with 1 equivalent of hydroxyl groups in component (A').

[0063] <(A2) Monomer Having Two or More Ethylenically Unsaturated Groups> The component (A2) is used primarily as a crosslinking agent for the component (A1). The photosensitive resin film of the present embodiment contains the component (A2) together with the component (A1), and therefore tends to increase the crosslinking density due to the photoradical polymerization reaction, improve the alkaline developer resistance and resolution, and form an interlayer insulating layer with superior heat resistance. The component (A2) may or may not have an acidic substituent.

[0064] The number of ethylenically unsaturated groups contained in the component (A2) is 2 or more, and from the viewpoint of resolution and of forming an interlayer insulating layer having superior heat resistance and dielectric properties, the number is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 7.

[0065] Examples of the component (A2) include a bifunctional monomer having two ethylenically unsaturated groups and a polyfunctional monomer having three or more ethylenically unsaturated groups.

[0066] Examples of bifunctional monomers having two ethylenically unsaturated groups include aliphatic di(meth)acrylates such as trimethylolpropane di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; di(meth)acrylates having an alicyclic skeleton such as dicyclopentadiene di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; and aromatic di(meth)acrylates such as 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane and bisphenol A diglycidyl ether di(meth)acrylate.

[0067] Examples of polyfunctional monomers having three or more ethylenically unsaturated groups include (meth)acrylate compounds 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; (meth)acrylate compounds having a skeleton derived from ditrimethylolpropane, such as ditrimethylolpropane tetra(meth)acrylate; and (meth)acrylate compounds having a skeleton derived from diglycerin. Here, the "(meth)acrylate compound having a skeleton derived from XXX" (where XXX is the name of the compound) means an esterification product of XXX and (meth)acrylic acid, and the esterification product also includes a compound modified with an alkyleneoxy group.

[0068] Among the above options, from the viewpoints of resolution and forming an interlayer insulating layer with superior conductor adhesion, the component (A2) is preferably a polyfunctional monomer having three or more ethylenically unsaturated groups, and more preferably a (meth)acrylate compound having a skeleton derived from trimethylolpropane or a (meth)acrylate compound having a skeleton derived from dipentaerythritol.

[0069] The component (A) may or may not contain compounds other than the components (A1) and (A2). Examples of the components other than the components (A1) and (A2) include monofunctional monomers having one ethylenically unsaturated group and no acidic substituent.

[0070] (Content of component (A)) The content of component (A) in the photosensitive resin film of this embodiment is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer formed, it is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass %, based on the total amount of resin components in the photosensitive resin film. In this specification, the term "resin component" refers to a resin and a compound that forms a resin by a curing reaction. For example, in the photosensitive resin film of this embodiment, component (A), component (B), component (E), and component (F) are classified as resin components. On the other hand, components (C), (D), (G) and (H) are not included in the resin component.

[0071] When the photosensitive resin film of the present embodiment contains the component (A1), its content is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer formed, it is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %, based on the total amount of resin components in the photosensitive resin film.

[0072] When the photosensitive resin film of the present embodiment contains the component (A1) and the component (A2), the content of the component (A2) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer formed, it is preferably 10 to 90 parts by mass, more preferably 30 to 80 parts by mass, and even more preferably 50 to 70 parts by mass per 100 parts by mass of the component (A1) in the photosensitive resin film of the present embodiment.

[0073] (Content of component (A) in resin composition (1)) The content of component (A) in resin composition (1) is not particularly limited, but from the viewpoint of the resolution of the photosensitive resin film and the dielectric properties of the interlayer insulating layer formed, it is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass %, based on the total amount of resin components in resin composition (1).

[0074] When the resin composition (1) contains the component (A1), the content of the component (A1) in the resin composition (1) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer to be formed, it is preferably 5 to 70 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total amount of the resin components in the resin composition (1).

[0075] When the resin composition (1) contains the component (A1) and the component (A2), the content of the component (A2) in the resin composition (1) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer to be formed, it is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 40 parts by mass per 100 parts by mass of the component (A1) in the resin composition (1).

[0076] (Content of component (A) in resin composition (2)) The content of component (A) in resin composition (2) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer formed, it is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass %, based on the total amount of resin components in resin composition (2).

[0077] When the resin composition (2) contains the component (A1), the content of the component (A1) in the resin composition (2) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer to be formed, it is preferably 5 to 60 mass %, more preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %, based on the total amount of the resin components in the resin composition (2).

[0078] When the resin composition (2) contains the component (A1) and the component (A2), the content of the component (A2) in the resin composition (2) is not particularly limited, but from the viewpoint of resolution and the dielectric properties of the interlayer insulating layer to be formed, it is preferably 20 to 100 parts by mass, more preferably 40 to 90 parts by mass, and even more preferably 60 to 80 parts by mass per 100 parts by mass of the component (A1) in the resin composition (2).

[0079] <(B) Thermosetting resin> The (B) thermosetting resin is not particularly limited as long as it is a resin having thermosetting properties. When the photosensitive resin film of the present embodiment contains the thermosetting resin (B), the heat resistance of the interlayer insulating layer formed tends to be improved. The (B) thermosetting resin may be used alone or in combination of two or more kinds.

[0080] (B) Examples of the thermosetting resin include epoxy resins, isocyanate resins, maleimide resins, phenolic resins, cyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, vinyl resins, dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, and other known thermosetting resins.

[0081] Among the above options, from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, the photosensitive resin film of the present embodiment preferably contains, as component (B), one or more resins selected from the group consisting of epoxy resins, maleimide resins, allyl resins, and vinyl resins, and more preferably contains an epoxy resin.

[0082] (epoxy resin) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0083] Epoxy resins are also classified into various epoxy resins depending on the difference in main skeleton, and each of the above types of epoxy resins is further classified as follows: Specifically, epoxy resins include, for example, bisphenol-based epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; bisphenol-based novolac-type epoxy resins such as bisphenol A-type novolac-type epoxy resins and bisphenol F-type novolac-type epoxy resins; novolac-type epoxy resins other than the above bisphenol-based novolac-type epoxy resins, such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, and biphenyl novolac-type epoxy resins; phenol aralkyl-type epoxy resins; stilbene-type epoxy resins; epoxy resins; naphthalene skeleton-containing epoxy resins such as naphthol novolac epoxy resins, naphthol epoxy resins, naphthol aralkyl epoxy resins, and naphthylene ether epoxy resins; biphenyl epoxy resins; biphenyl aralkyl epoxy resins; xylylene epoxy resins; dihydroanthracene epoxy resins; alicyclic epoxy resins such as saturated dicyclopentadiene epoxy resins; heterocyclic epoxy resins; spiro ring-containing epoxy resins; cyclohexanedimethanol epoxy resins; trimethylol epoxy resins; aliphatic linear epoxy resins; and rubber-modified epoxy resins.

[0084] Among these, the epoxy resin is preferably a bisphenol-based epoxy resin, a naphthalene skeleton-containing epoxy resin, or a biphenylaralkyl-type epoxy resin, and more preferably a naphthalene skeleton-containing epoxy resin or a biphenylaralkyl-type epoxy resin.

[0085] (Isocyanate resin) Examples of isocyanate resins include aliphatic isocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic isocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, and norbornane diisocyanate; aromatic isocyanates such as xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate; biuret derivatives thereof; and nurate derivatives thereof. Among these, aliphatic isocyanates are preferred, and hexamethylene diisocyanate is more preferred.

[0086] (maleimide resin) Examples of maleimide resins include aromatic maleimide compounds having an N-substituted maleimide group directly bonded to an aromatic ring, aliphatic maleimide compounds having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon group, etc. Among these, from the viewpoints of heat resistance and handleability, aromatic maleimide compounds are preferred, and aromatic bismaleimide compounds are more preferred. Examples of aromatic maleimide compounds include bis(4-maleimidophenyl)methane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, biphenylaralkyl-type maleimide resin, aromatic bismaleimide resin having an indane skeleton, etc. Among these, aromatic bismaleimide resin having an indane skeleton is preferred.

[0087] (allyl resin) Examples of allyl resins include allyl group-containing isocyanurates such as diallyl isocyanurate and triallyl isocyanurate; allyl group-containing cyanurates such as diallyl cyanurate and triallyl cyanurate; 1,3,4,6-tetraallyl glycoluril, etc. Among these, from the viewpoints of heat resistance, dielectric properties, and handleability, allyl group-containing isocyanurates are preferred, and diallyl isocyanurate is more preferred.

[0088] ((B) Component Content) The content of the (B) thermosetting resin in the photosensitive resin film of this embodiment is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior conductor adhesion and heat resistance, it is preferably 1 to 60 mass %, more preferably 10 to 50 mass %, and even more preferably 20 to 40 mass %, based on the total amount of resin components in the photosensitive resin film.

[0089] When the photosensitive resin film of this embodiment contains an epoxy resin as the (B) thermosetting resin, its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in conductor adhesion, heat resistance, and dielectric properties, it is preferably 1 to 50 mass %, more preferably 2 to 30 mass %, and even more preferably 3 to 25 mass %, based on the total amount of resin components in the photosensitive resin film.

[0090] When the photosensitive resin film of this embodiment contains an isocyanate resin as the (B) thermosetting resin, its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in conductor adhesion, heat resistance, and dielectric properties, it is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and even more preferably 4 to 10 mass %, based on the total amount of resin components in the photosensitive resin film.

[0091] When the photosensitive resin film of the present embodiment contains a maleimide resin as the (B) thermosetting resin, its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in conductor adhesion, heat resistance, and dielectric properties, it is preferably 1 to 40 mass %, more preferably 3 to 30 mass %, and even more preferably 5 to 20 mass %, based on the total amount of resin components in the photosensitive resin film.

[0092] (Content of component (B) in resin composition (1)) The content of the thermosetting resin (B) in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior conductor adhesion and heat resistance, it is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 70 mass %, based on the total amount of resin components in the resin composition (1).

[0093] When the resin composition (1) contains an epoxy resin as the (B) thermosetting resin, the content of the epoxy resin in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior conductor adhesion and heat resistance, it is preferably 7 to 80 mass %, more preferably 15 to 70 mass %, and even more preferably 20 to 60 mass %, based on the total amount of resin components in the resin composition (1). The content of the epoxy resin in the resin composition (1) by mass is preferably greater than the content of the epoxy resin in the resin composition (2) by mass, from the viewpoint of forming an interlayer insulating layer having superior adhesion to the conductor.

[0094] When the resin composition (1) contains an isocyanate resin as the (B) thermosetting resin, the content of the isocyanate resin in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior conductor adhesion and heat resistance, it is preferably 1 to 30 mass %, more preferably 3 to 20 mass %, and even more preferably 5 to 15 mass %, based on the total amount of resin components in the resin composition (1).

[0095] (Content of component (B) in resin composition (2)) The content of the thermosetting resin (B) in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and dielectric properties, it is preferably 1 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 20 to 30 mass %, based on the total amount of resin components in the resin composition (2).

[0096] When the resin composition (2) contains an epoxy resin as the (B) thermosetting resin, the content of the epoxy resin in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having better heat resistance and dielectric properties, it is preferably 1 to 50 mass %, more preferably 5 to 30 mass %, and even more preferably 7 to 15 mass %, based on the total amount of resin components in the resin composition (2).

[0097] When the resin composition (2) contains an isocyanate resin as the (B) thermosetting resin, the content of the isocyanate resin in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having better heat resistance and dielectric properties, it is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and even more preferably 4 to 10 mass %, based on the total amount of resin components in the resin composition (2).

[0098] When the resin composition (2) contains a maleimide resin as the (B) thermosetting resin, the content of the maleimide resin in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having more excellent heat resistance and dielectric properties, it is preferably 1 to 40 mass %, more preferably 3 to 30 mass %, and even more preferably 5 to 20 mass %, based on the total amount of resin components in the resin composition (2).

[0099] <(C) Photopolymerization initiator> The photopolymerization initiator (C) is a polymerization initiator for the photoradical polymerization reaction of the ethylenically unsaturated group contained in the component (A). The photosensitive resin film of the present embodiment tends to have a further improved resolution due to the inclusion of the photopolymerization initiator (C). The (C) photopolymerization initiator may be used alone or in combination of two or more kinds.

[0100] Examples of the (C) photopolymerization initiator include benzoin-based compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone-based compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane, and N,N-dimethylaminoacetophenone; anthraquinone-based compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketal-based compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 9- Acridine compounds such as phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) and oxime ester compounds such as 1-phenyl-1,2-propanedione-2-[O-(ethoxycarbonyl)oxime]; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; and benzophenone compounds such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. Among these, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime) are preferred.

[0101] ((C) Component Content) The content of the (C) photopolymerization initiator in the photosensitive resin film of this embodiment is not particularly limited, but from the viewpoint of easily obtaining a moderate effect of promoting the polymerization reaction, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass per 100 parts by mass of the (A) component in the photosensitive resin film.

[0102] (Content of component (C) in resin composition (1)) The content of the (C) photopolymerization initiator in the resin composition (1) is not particularly limited, but from the viewpoint of easily obtaining a suitable effect of promoting the polymerization reaction, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass per 100 parts by mass of the (A) component in the resin composition (1).

[0103] (Content of component (C) in resin composition (2)) The content of the (C) photopolymerization initiator in the resin composition (2) is not particularly limited, but from the viewpoint of easily obtaining a suitable effect of promoting the polymerization reaction, it is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 1 part by mass per 100 parts by mass of the (A) component in the resin composition (2).

[0104] <(D) Inorganic filler> When the photosensitive resin film of the present embodiment contains the inorganic filler (D), the interlayer insulating layer formed therefrom tends to have further improved low thermal expansion properties, heat resistance, and flame retardancy. The (D) inorganic filler may be used alone or in combination of two or more kinds.

[0105] From the viewpoint of exhibiting high adhesive strength with plated copper, the photosensitive resin film of this embodiment preferably contains silica as the inorganic filler (D).

[0106] Examples of silica include precipitated silica produced by a wet method and having a high water content, and dry-process silica produced by a dry method and containing almost no bound water, etc. Furthermore, examples of dry-process silica include crushed silica, fumed silica, fused silica, etc., depending on the production method. The silica may be surface-treated with a coupling agent such as a silane coupling agent.

[0107] As the silica, for example, (D1) a true density of 1,500 kg / m 3 (D2) Silica with a true density of 1,500 kg / m or more (hereinafter referred to as "component (D1)"). 3 Examples include the following silica (hereinafter also referred to as "component (D2)").

[0108] The component (D1) tends to have a low dielectric loss tangent, and therefore, from the viewpoint of forming an interlayer insulating layer with more excellent dielectric properties, the resin composition (1) preferably contains the component (D1). The true density of the silica (D1) component is preferably greater than 1,500 and less than 2,200 kg / m from the viewpoint of low thermal expansion. 3 or less, more preferably 1,600 to 2,200 kg / m 3 , and more preferably 1,800 to 2,200 kg / m 3 is.

[0109] The component (D2) tends to have a small relative dielectric constant, and therefore, from the viewpoint of forming an interlayer insulating layer with more excellent dielectric properties, the resin composition (2) preferably contains the component (D2). The true density of the silica (D2) component is preferably 1,000 to 1,500 kg / m from the viewpoint of dielectric properties. 3 , more preferably 1,100 to 1,500 kg / m 3 , and more preferably 1,200 to 1,500 kg / m 3 , particularly preferably 1,250 to 1,450 kg / m 3 , and most preferably 1,250 to 1,400 kg / m 3 is. The true density of silica can be measured using a dry automatic density meter "AccuPycII 1340" (manufactured by Shimadzu Corporation).

[0110] Examples of (D) inorganic fillers other than silica include alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, and silicon carbide.

[0111] (D) Volume average particle diameter of inorganic filler (D 50 ) is not particularly limited, but from the viewpoint of resolution, it is preferably 0.01 to 3.0 μm, more preferably 0.1 to 2.5 μm, and even more preferably 0.3 to 2.0 μm. In this specification, the volume average particle diameter (D 50 ) can be determined as the particle diameter corresponding to the cumulative value of 50% (volume basis) in the particle size distribution by measuring particles dispersed in a solvent with a refractive index of 1.38 using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., product name: N5) in accordance with the international standard ISO 13321.

[0112] ((D) Component Content) The content of the (D) inorganic filler in the photosensitive resin film of this embodiment is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, it is preferably 2 to 60 mass%, more preferably 2 mass% or more but less than 60 mass%, even more preferably 3 to 55 mass%, still more preferably 4 to 50 mass%, even more preferably 5 to 40 mass%, and particularly preferably 6 to 25 mass%.

[0113] The content of silica in the photosensitive resin film of this embodiment is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, it is preferably 2 to 60 mass%, more preferably 2 mass% or more but less than 60 mass%, even more preferably 3 to 55 mass%, even more preferably 4 to 50 mass%, even more preferably 5 to 40 mass%, and particularly preferably 6 to 25 mass%.

[0114] When the photosensitive resin film of the present embodiment contains the component (D1), its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, it is preferably 10 to 100 mass%, more preferably 20 to 90 mass%, and even more preferably 30 to 80 mass%, relative to the total amount (100 mass%) of the inorganic filler (D) in the photosensitive resin film.

[0115] When the photosensitive resin film of the present embodiment contains the component (D2), its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, and flame retardancy, it is preferably 5 to 90 mass%, more preferably 10 to 80 mass%, and even more preferably 20 to 70 mass%, relative to the total amount (100 mass%) of the component (D) in the photosensitive resin film.

[0116] (Content of (D) inorganic filler in resin composition (1)) The content of the (D) inorganic filler in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, it is preferably 5 to 70 mass %, more preferably 15 to 60 mass %, and even more preferably 25 to 50 mass %, based on the total solid content of the resin composition (1).

[0117] When the resin composition (1) contains silica, the content of silica in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, the content of silica is preferably 5 to 70 mass %, more preferably 15 to 60 mass %, and even more preferably 25 to 50 mass %, based on the total solid content of the resin composition (1). The content of silica in resin composition (1) by mass is preferably greater than the content of silica in resin composition (2) by mass, from the viewpoint of forming an interlayer insulating layer having superior conductor adhesion.

[0118] When the resin composition (1) contains the (D1) component, the content of the (D1) component in the resin composition (1) is not particularly limited, but is preferably 60 to 100 mass %, more preferably 70 to 100 mass %, and even more preferably 80 to 100 mass %, relative to the total amount (100 mass %) of the (D) inorganic filler in the resin composition (1), from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion.

[0119] (Content of (D) inorganic filler in resin composition (2)) The content of the (D) inorganic filler in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having low thermal expansion, heat resistance, and flame retardancy, it is preferably less than 60 mass%, more preferably 1 to 55 mass%, even more preferably 2 to 50 mass%, even more preferably 3 to 30 mass%, and particularly preferably 5 to 20 mass%, based on the total solid content of the resin composition (2).

[0120] When the resin composition (2) contains silica, the content of silica in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, flame retardancy, and conductor adhesion, the content of silica is preferably less than 60 mass%, more preferably 1 to 55 mass%, even more preferably 2 to 50 mass%, still more preferably 3 to 30 mass%, and particularly preferably 5 to 20 mass%, based on the total solid content of the resin composition (2).

[0121] When the resin composition (2) contains the (D2) component, the content of the (D2) component in the resin composition (2) is not particularly limited, but is preferably 60 to 100 mass %, more preferably 70 to 100 mass %, and even more preferably 80 to 100 mass %, relative to the total amount (100 mass %) of the (D) component in the resin composition (2), from the viewpoint of forming an interlayer insulating layer that is superior in low thermal expansion, heat resistance, and flame retardancy.

[0122] <(E) Fluorine-containing resin> By including the fluorine-containing resin (E) in the photosensitive resin film of this embodiment, the interlayer insulating layer formed from the photosensitive resin film of this embodiment tends to have a reduced relative dielectric constant. The (E) fluorine-containing resin may be used alone or in combination of two or more kinds.

[0123] (E) fluorine-containing resins include, for example, polymers of olefins containing fluorine atoms (hereinafter also referred to as "fluorine-containing olefins"). The fluorine-containing olefin may be an olefin in which some of the hydrogen atoms in carbon-hydrogen bonds have been substituted with fluorine atoms, but from the viewpoint of further reducing the dielectric constant, an olefin in which the hydrogen atoms in all of the carbon-hydrogen bonds have been substituted with fluorine atoms is preferred.

[0124] (E) Examples of fluorine-containing resins include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyvinyl fluoride, polyvinylidene fluoride, etc. Among these, polytetrafluoroethylene is preferred.

[0125] (E) The fluorine-containing resin is preferably in the form of particles. The volume average particle diameter (D 50 ) is not particularly limited, but from the viewpoint of resolution, it is preferably 0.01 to 3.0 μm, more preferably 0.05 to 2.5 μm, and even more preferably 0.1 to 2.0 μm.

[0126] (Content of component (E)) The content of the fluorine-containing resin (E) in the photosensitive resin film of the present embodiment is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and adhesion to a conductor, it is preferably 5 to 60 mass %, more preferably 10 to 45 mass %, and even more preferably 20 to 35 mass %, based on the total amount of resin components in the photosensitive resin film.

[0127] (Content of component (E) in resin composition (1)) The resin composition (1) may contain (E) a fluorine-containing resin. However, from the viewpoint of resolution and forming an interlayer insulating layer having superior adhesion to a conductor, it is preferable that the resin composition (1) does not contain (E) a fluorine-containing resin. When the resin composition (1) contains the fluorine-containing resin (E), the content of the fluorine-containing resin (E) in the resin composition (1) is preferably as small as possible, and from the same viewpoint as above, it is preferably 20 mass % or less, more preferably 10 mass % or less, and even more preferably 1 mass % or less, based on the total amount of the resin components in the resin composition (1).

[0128] (Content of component (E) in resin composition (2)) The content of the fluorine-containing resin (E) in the resin composition (2) is not particularly limited, but from the viewpoint of resolution and of forming an interlayer insulating layer that is superior in insulation reliability, relative dielectric constant, heat resistance, and conductor adhesion, it is preferably 10 to 70 mass%, more preferably 20 to 50 mass%, and even more preferably 25 to 40 mass%, based on the total amount of resin components in the resin composition (2).

[0129] <(F) Elastomer> The photosensitive resin film of the present embodiment may further contain an elastomer (F). When the photosensitive resin film of this embodiment contains the elastomer (F), the interlayer insulating layer formed therefrom tends to have further improved adhesion to the conductor. The term "elastomer" used herein refers to a polymer having a glass transition temperature of 25°C or lower as measured by differential scanning calorimetry in accordance with JIS K 6240:2011. The (F) elastomer may be used alone or in combination of two or more kinds.

[0130] Examples of the (F) elastomer include polybutadiene-based elastomers, polyester-based elastomers, styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, derivatives of these elastomers, etc. Among these, polybutadiene-based elastomers are preferred from the viewpoints of compatibility with the resin component and of forming an interlayer insulating layer having superior conductor adhesion.

[0131] Suitable examples of polybutadiene elastomers include those containing 1,2-vinyl groups derived from 1,3-butadiene. From the viewpoint of resolution, the polybutadiene elastomer is preferably a polybutadiene elastomer having an acid anhydride group, and more preferably a polybutadiene elastomer having an acid anhydride group derived from maleic anhydride. When the polybutadiene-based elastomer has acid anhydride groups, the number of acid anhydride groups in one molecule is not particularly limited, but from the viewpoint of resolution and forming an interlayer insulating layer with a more excellent relative dielectric constant, it is preferably 1 to 12, more preferably 3 to 11, and even more preferably 6 to 10.

[0132] The number average molecular weight (Mn) of the (F) elastomer is not particularly limited, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, even more preferably 3,000 to 10,000, and particularly preferably 4,000 to 7,000. In this specification, the number average molecular weight (Mn) is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted into standard polystyrene, and more specifically, is a value measured according to the method described in the examples.

[0133] ((F) Component Content) The content of the (F) elastomer in the photosensitive resin film of the present embodiment is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, it is preferably 0.5 to 20 mass %, more preferably 1 to 15 mass %, and even more preferably 2 to 10 mass %, based on the total amount of resin components in the photosensitive resin film.

[0134] (Content of component (F) in resin composition (1)) When the resin composition (1) contains the elastomer (F), the content of the elastomer (F) in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, it is preferably 1 to 30 mass %, more preferably 3 to 20 mass %, and even more preferably 5 to 15 mass %, based on the total amount of resin components in the resin composition (1).

[0135] (Content of component (F) in resin composition (2)) When the resin composition (2) contains the elastomer (F), the content of the elastomer (F) in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, it is preferably 0.5 to 20 mass%, more preferably 1 to 15 mass%, and even more preferably 2 to 10 mass%, based on the total amount of resin components in the resin composition (2).

[0136] <(G)Organic peroxide> The photosensitive resin film of this embodiment preferably further contains (G) an organic peroxide, which is a polymerization initiator for the thermal radical polymerization reaction of the ethylenically unsaturated groups contained mainly in component (A) and, if necessary, in component (B). When the photosensitive resin film of the present embodiment contains (G) an organic peroxide, the interlayer insulating layer formed therefrom tends to have further improved heat resistance, dielectric properties, and the like. The (G) organic peroxides may be used alone or in combination of two or more.

[0137] (G) Examples of organic peroxides include peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, 2,2-di(4,4-di-t-butylperoxycyclohexyl)propane, and 1,1-di(t-amylperoxy)cyclohexane; hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; alkyl peroxides such as t-butyl peroxyacetate and t-amylperoxyisononanoate; t-butylcumyl peroxide and di-t-butyl Examples of the peroxides include dialkyl peroxides such as butyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, and 1,3-di(t-butylperoxyisopropyl)benzene; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butylperoxyisopropyl monocarbonate; peroxycarbonates such as t-butylperoxyisopropyl carbonate and polyether tetrakis(t-butylperoxycarbonate); and diacyl peroxides such as dibenzoyl peroxide. Among these, 1,3-di(t-butylperoxyisopropyl)benzene is preferred.

[0138] ((G) Component Content) When the photosensitive resin film of the present embodiment contains (G) an organic peroxide, its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer that is superior in heat resistance and adhesion to a conductor, it is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1.5 to 4 parts by mass per 100 parts by mass of the (A) component in the photosensitive resin film.

[0139] (Content of component (G) in resin composition (1)) When the resin composition (1) contains an organic peroxide (G), the content of the organic peroxide (G) in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and adhesion to a conductor, the content is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1.5 to 4 parts by mass per 100 parts by mass of the component (A) in the resin composition (1).

[0140] (Content of component (G) in resin composition (2)) When the resin composition (2) contains an organic peroxide (G), the content of the organic peroxide (G) in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and adhesion to a conductor, the content is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1.5 to 4 parts by mass per 100 parts by mass of the component (A) in the resin composition (2).

[0141] <(H) Curing accelerator> The photosensitive resin film of the present embodiment preferably further contains (H) a curing accelerator. When the photosensitive resin film of the present embodiment contains the curing accelerator (H), the heat resistance, dielectric properties, and the like of the interlayer insulating layer formed tend to be further improved. The (H) curing accelerator may be used alone or in combination of two or more kinds.

[0142] (H) Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-1-benzyl-1H-imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and isocyanate-masked imidazole (an addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole); trimethylamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol), and tetramethylamine. tertiary amines such as trimethylguanidine and m-aminophenol; 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-mentioned polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and the like. Among these, imidazole compounds are preferred from the viewpoint of obtaining an excellent curing effect.

[0143] (Content of component (H)) When the photosensitive resin film of the present embodiment contains the curing accelerator (H), its content is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, it is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 4 parts by mass per 100 parts by mass of the component (B) in the photosensitive resin film.

[0144] (Content of component (H) in resin composition (1)) When the resin composition (1) contains the curing accelerator (H), the content of the curing accelerator (H) in the resin composition (1) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, the content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 4 parts by mass per 100 parts by mass of the component (B) in the resin composition (1).

[0145] (Content of component (H) in resin composition (2)) When the resin composition (2) contains the curing accelerator (H), the content of the curing accelerator (H) in the resin composition (2) is not particularly limited, but from the viewpoint of forming an interlayer insulating layer having superior heat resistance and conductor adhesion, the content is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 5 parts by mass per 100 parts by mass of the component (B) in the resin composition (2).

[0146] <(I) Other ingredients> The photosensitive resin film of the present embodiment may contain components other than the above-mentioned components as (I) other components, if necessary. Examples of (I) other components include resins other than the above components; organic fillers other than component (E); photosensitizers; polymerization inhibitors; foam stabilizers; pigments; adhesion aids such as melamine; foam stabilizers such as silicone compounds; thickeners; and flame retardants. These may be used singly or in combination of two or more. The content of (I) other components in the photosensitive resin film of this embodiment may be adjusted appropriately depending on each purpose, and may be 0.01 to 10 mass %, 0.05 to 5 mass %, or 0.1 to 1 mass % for each.

[0147] <Method for producing photosensitive resin film> The photosensitive resin film of the present embodiment can be produced using, for example, resin composition (1) and resin composition (2). Resin composition (1) and resin composition (2) can be produced by mixing the components to be incorporated into each layer and a diluent to be used as needed. For mixing the components, for example, a roll mill, a bead mill, a planetary mixer, a planetary mixer, a planetary mixer, or a planetary mixer can be used.

[0148] The resin composition (1) and the resin composition (2) are applied to separate carrier films and dried as necessary to form a resin composition (1) film with a carrier film and a resin composition (2) film with a carrier film. Next, the resin composition films of the resin composition (1) film with a carrier film and the resin composition (2) film with a carrier film are bonded together to produce a photosensitive resin film having carrier films on both sides.

[0149] Alternatively, the photosensitive resin film of the present embodiment can be produced by coating one of the resin compositions on a carrier film and then coating the other of the resin compositions on the first resin composition. After coating one of the resin compositions, drying may be performed as necessary before coating the other resin composition.

[0150] Examples of methods for applying the resin composition (1) and the resin composition (2) include methods using a coating device such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, or a die coater. The drying temperature when drying the coating films of the resin compositions (1) and (2) is not particularly limited, but is preferably 60 to 150° C., more preferably 70 to 120° C., and even more preferably 80 to 100° C. The drying time is also not particularly limited, but is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes.

[0151] Examples of materials for the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film is not particularly limited, but is preferably 5 to 100 μm, more preferably 10 to 60 μm, and even more preferably 15 to 45 μm.

[0152] [Printed wiring board and its manufacturing method] The printed wiring board of this embodiment is a printed wiring board having an interlayer insulating layer that is a cured product of the photosensitive resin film of this embodiment. The "interlayer insulating layer" of the printed wiring board of this embodiment also includes the state after various processing or treatments such as via and wiring formation and roughening treatment have been performed.

[0153] The method for producing a printed wiring board of this embodiment is not particularly limited as long as it is a method that uses the photosensitive resin film of this embodiment, but a method for producing a printed wiring board that includes the following (1) to (4) is preferred. (1): Laminating the photosensitive resin film of the present embodiment onto one or both surfaces of a circuit board with the second surface serving as an attachment surface (hereinafter also referred to as "laminating step (1)"). (2): Forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in (1) above (hereinafter also referred to as "via forming step (2)"). (3): The interlayer insulating layer having the vias is heat-cured (hereinafter also referred to as "heat-curing step (3)"). (4) Forming a circuit pattern on the surface of the interlayer insulating layer opposite to the circuit board (hereinafter also referred to as "circuit pattern forming step (4)"). Hereinafter, the method for manufacturing a printed wiring board according to this embodiment will be described with reference to FIG. In this specification, for convenience, a specific operation may be referred to as "XX step", but the "XX step" is not limited to only the embodiments specifically described in this specification.

[0154] (Lamination process (1)) In the laminating step (1), the photosensitive resin film of this embodiment is laminated onto one or both surfaces of a circuit board with the second surface serving as an attachment surface. FIG. 1(a) illustrates a process of forming a photosensitive layer 103 on both sides of a substrate 101 having a circuit pattern 102. The photosensitive layer 103 can be formed by laminating the photosensitive resin film of this embodiment onto both sides of the substrate 101 so that the second surface becomes the attachment surface. The lamination may be performed by, for example, pressing the laminate together under pressure and heat using a vacuum laminator or the like. After lamination, if a carrier film is attached to the photosensitive layer 103, the carrier film may be peeled off before or after exposure, which will be described later.

[0155] (Via formation process (2)) In the via forming step (2), the photosensitive layer formed in the laminating step (1) is exposed to light and developed to form an interlayer insulating layer having vias. FIG. 1( b ) illustrates a process of forming an interlayer insulating layer 104 having a via 105 by exposing and developing the photosensitive layer 103 . By exposing the photosensitive layer 103 to light, a photoradical polymerization reaction is initiated, and the photosensitive resin film is cured.

[0156] The exposure method for the photosensitive layer 103 may be, for example, a mask exposure method in which actinic rays are irradiated in an imagewise manner through a negative or positive mask pattern called artwork, or a method in which actinic rays are irradiated in an imagewise manner by a direct writing exposure method such as an LDI (Laser Direct Imaging) exposure method or a DLP (Digital Light Processing) exposure method. Examples of light sources for actinic rays include known light sources that effectively emit ultraviolet or visible light, such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and gas lasers such as argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers. The exposure dose may be adjusted appropriately depending on the light source used, the thickness of the photosensitive layer, etc. For example, when a photosensitive layer having a thickness of 1 to 100 μm is exposed to ultraviolet radiation from a high-pressure mercury lamp, the exposure dose is not particularly limited, but is preferably 10 to 1,000 mJ / cm. 2 , more preferably 50 to 700 mJ / cm 2 , and more preferably 150 to 400 mJ / cm 2 is.

[0157] Next, if a carrier film is present on the photosensitive layer 103, the carrier film is removed before development. In the development, the uncured portions of the photosensitive layer 103 are removed, and the photocured portions are formed as the interlayer insulating layer 104 on the substrate. The development method may be wet development or dry development, but wet development is preferred. As a wet development method, a spray method is preferred from the viewpoint of improving resolution. Examples of the developer include an alkaline aqueous solution, a water-based developer, and an organic solvent-based developer, and among these, an alkaline aqueous solution is preferred. After the exposure and development, post-exposure may be carried out in order to increase the degree of hardening of the interlayer insulating layer. The exposure dose in the post-exposure is not particularly limited, but is preferably 0.2 to 10 J / cm. 2 , more preferably 0.5 to 5 J / cm 2 is.

[0158] The shape of the via is not particularly limited, and examples of cross-sectional shapes include a rectangle, an inverted trapezoid, etc. Note that an inverted trapezoid has a shape in which the upper side is longer than the lower side. Examples of shapes in a plan view include a circle, a rectangle, etc. The photolithography method of this embodiment allows the formation of vias with an inverted trapezoidal cross section, which is preferable because the plating copper has a high adhesion to the via wall surface. In the formation of vias by the photolithography method of this embodiment, the diameter of the vias can be smaller than the diameter of vias formed by laser processing. The diameter of the vias formed by the manufacturing method of this embodiment may be, for example, 40 μm or less, 35 μm or less, or 30 μm or less. There is no particular restriction on the lower limit of the via diameter, but it may be, for example, 15 μm or more, or 20 μm or more.

[0159] (Heat curing process (3)) In the heat curing step (3), the interlayer insulating layer having the vias is heat cured. That is, in the heat curing step (3), the curing reaction of the thermosetting component contained in the photosensitive resin film of the present embodiment is promoted by heating. The heating temperature is not particularly limited, but is preferably 100 to 300° C., more preferably 120 to 200° C., and even more preferably 150 to 180° C. The heating time is not particularly limited, but is preferably 0.3 to 3 hours, more preferably 0.5 to 2 hours, and even more preferably 0.75 to 1.5 hours.

[0160] (Circuit pattern formation process (4)) Next, a circuit pattern is formed on the surface of the interlayer insulating layer formed above opposite to the circuit board. The surface of the interlayer insulating layer opposite to the circuit board corresponds to the first surface after curing. From the viewpoint of forming fine wiring, the circuit pattern is preferably formed by a semi-additive process in which roughening treatment, formation of a seed layer, formation of a resist pattern, formation of a copper circuit layer, and removal of the resist pattern are carried out in this order.

[0161] The roughening treatment is a treatment for roughening the surface of the interlayer insulating layer to form uneven anchors. If smears occur in the via formation step (2), roughening treatment and smear removal may be performed simultaneously using a roughening solution. Examples of roughening solutions include alkaline permanganate roughening solutions such as sodium permanganate roughening solutions; chromium / sulfuric acid roughening solutions; and sodium fluoride / chromium / sulfuric acid roughening solutions.

[0162] FIG. 1(c) illustrates the step of forming a seed layer 106. The seed layer 106 is for forming a power supply layer for electrolytic copper plating. The seed layer 106 can be formed by performing electroless copper plating on the via bottom, via wall surface, and the entire surface of the interlayer insulating layer using a palladium catalyst or the like.

[0163] FIG. 1( d ) illustrates the step of forming a resist pattern 107 on the seed layer 106 . The resist pattern 107 can be formed, for example, by thermocompressing a dry film resist onto the seed layer 106 using a roll laminator or the like, and then exposing and developing the resist. Commercially available dry film resists can be used.

[0164] The dry film resist may be exposed through a mask on which a desired wiring pattern is drawn. After exposure, the dry film resist is developed using an alkaline aqueous solution to remove the unexposed portions, forming a resist pattern 107. Thereafter, plasma treatment may be performed as necessary to remove development residues of the dry film resist.

[0165] FIG. 1(e) illustrates the step of forming a copper circuit layer 108. The copper circuit layer 108 is preferably formed by electrolytic copper plating. As the electrolytic copper plating solution used for the electrolytic copper plating, for example, a commercially available electrolytic copper plating solution such as an electrolytic copper plating solution containing copper sulfate can be used. After the electrolytic copper plating, the resist pattern 107 is removed using an alkaline aqueous solution or an amine-based remover, and then flash etching is performed to remove the seed layer 106 between the wirings, the palladium catalyst is removed, etc. If necessary, a post-baking treatment may be performed to sufficiently heat-cure any unreacted thermosetting components.

[0166] FIG. 1(f) shows a multilayer printed wiring board 100A that has been multilayered by repeating the above steps and has a solder resist layer 109 on the outermost surface. The solder resist layer 109 can be formed using a known photosensitive resin film for solder resist.

[0167] The method for manufacturing a printed wiring board in which vias are formed using the photosensitive resin film of this embodiment has been described above, but the photosensitive resin film of this embodiment has excellent pattern resolution, so it is also suitable for forming cavities for incorporating chips, passive elements, etc. The cavities can be suitably formed, for example, by using a drawing pattern that can form the desired cavities when forming a pattern by exposing the photosensitive resin film in the above description of the printed wiring board.

[0168] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package having the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured by, for example, mounting semiconductor elements such as semiconductor chips and memories at predetermined positions on the printed wiring board of this embodiment and sealing the semiconductor elements with sealing resin or the like. [Example]

[0169] The present embodiment will be described in more detail below with reference to examples, but the present embodiment is not limited to these examples.

[0170] [Acid value measurement method] The acid value was calculated from the amount of potassium hydroxide aqueous solution required to neutralize the object to be measured.

[0171] [Method for measuring weight average molecular weight (Mw) and number average molecular weight (Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured using the following GPC measurement device and measurement conditions, and calculated using a calibration curve of standard polystyrene. The calibration curve was created using a set of five standard polystyrene samples ("PStQuick MP-H" and "PStQuick B", manufactured by Tosoh Corporation). (GPC measurement device) GPC equipment: High-speed GPC equipment "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation Column: TSKgel SuperMultipore HZ-H column (column length: 15 cm, column inner diameter: 4.6 mm), manufactured by Tosoh Corporation (Measurement conditions) Solvent: tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35ml / min Sample concentration: 10mg / THF5ml Injection volume: 20μl

[0172] [Method for measuring weight loss due to roughening treatment] The copper foil surface of a printed wiring board substrate (Showa Denko Materials Co., Ltd., product name "MCL-E-679"), which had a copper foil (12 μm thick) laminated to a glass epoxy base, was pre-roughened with a pre-roughening solution (MEC Co., Ltd., product name "CZ-8100"), followed by rinsing with water and drying. Next, the carrier film on the first or second surface of the carrier-film-attached photosensitive resin film produced in each example was peeled off, and the exposed first or second surface was laminated onto the copper foil of the pre-roughened printed wiring board substrate. Lamination was performed using a press-type vacuum laminator (Meiki Seisakusho Co., Ltd., product name "MVLP-500") under the following conditions: press hot plate temperature 70°C, vacuum time 20 seconds, lamination press time 30 seconds, atmospheric pressure 4 kPa or less, and pressure 0.4 MPa. After lamination, the laminate was left at room temperature for at least 1 hour to obtain a laminate for evaluation in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil of the substrate for printed wiring board. With the carrier film of the laminate for evaluation still attached, a flat exposure machine was used to expose the laminate to a light intensity of 400 mJ / cm. 2 The laminate was then irradiated with ultraviolet light (wavelength 365 nm). The carrier film was then peeled off and removed, and the laminate was exposed to an exposure dose of 2 J / cm using a UV conveyor device (manufactured by Oak Manufacturing Co., Ltd.) with a high-pressure mercury lamp. 2 The laminate was then heated at 170°C for 1 hour using a hot air circulation dryer to obtain evaluation laminate (1) in which the first surface was exposed and the second surface was not exposed, and evaluation laminate (2) in which the second surface was exposed and the first surface was not exposed. The heated evaluation laminates (1) and (2) were subjected to a roughening treatment according to the following procedure. The laminate to be roughened was immersed in a swelling solution (aqueous solution containing Swelling Dip Securigant P at a concentration of 49.85% by mass and sodium hydroxide at 0.3% by mass) at 70°C for 5 minutes, then in an oxidizing solution (aqueous solution containing Dosing Securigant P500J at a concentration of 14.55% by mass and sodium hydroxide at 3.69% by mass) at 80°C for 15 minutes, and then in a neutralizing solution (aqueous solution containing Reduction Conditioner Securigant P500 at a concentration of 10.65% by mass and 95% sulfuric acid at 8.27% by mass) at 50°C for 5 minutes, and then dried at 105°C for 10 minutes. In the roughening treatment of each layer, the weight loss of the evaluation laminate (1) and the evaluation laminate (2) was calculated from the difference between the dry weight before the roughening treatment and the dry weight after the roughening treatment. The weight loss of the evaluation laminate (1) was defined as the weight loss of the first surface a, and the weight loss of the evaluation laminate (2) was defined as the weight loss of the second surface b, and the ratio [a / b] of the two was calculated.

[0173] [Production of photosensitive resin film] Examples 1 to 7, Comparative Examples 1 to 2 The components were blended according to the formulation shown in Table 1 (the units of values ​​in the table are parts by mass, and in the case of a solution, they are solid content equivalents), and kneaded using a three-roll mill and a planetary mixer. Methyl ethyl ketone was then added so that the solid content concentration became 65% by mass, and resin compositions (1) and (2) were obtained, respectively. Next, the resin composition (1) was applied onto a carrier film (PET film, manufactured by Teijin Limited, product name "G2-16", thickness 16 μm) and dried at 100°C for 10 minutes using a hot air convection dryer to form a resin composition (1) film with a carrier film (resin composition (1) film thickness 5 μm). In addition, resin composition (2) was applied to a carrier film (PET film manufactured by Teijin Limited, product name "G2-16", thickness 16 μm) different from the above, and dried at 100°C for 10 minutes using a hot air convection dryer to form a resin composition (2) film with a carrier film (resin composition (2) film thickness 20 μm). The resin composition films of the resin composition (1) film with a carrier film and the resin composition (2) film with a carrier film obtained above were bonded together to obtain a photosensitive resin film with a carrier film (photosensitive resin film thickness: 25 μm).

[0174] The photosensitive resin films thus produced were subjected to the following evaluations. The evaluation results are shown in Table 2 together with the content of each component in the photosensitive resin film.

[0175] [Measurement of relative permittivity (Dk) and dielectric loss tangent (Df)] Two photosensitive resin films with a carrier film produced in each example were prepared by peeling off the carrier film on the second surface side, and the second surfaces were attached to each other. Next, with both sides of the carrier film still attached, a flat exposure machine was used to expose the film to a light intensity of 400 mJ / cm 2 The carrier films on both sides were then peeled off and the film was exposed to ultraviolet light at a dose of 2 J / cm using a UV conveyor-type exposure machine. 2 The specimen was irradiated with ultraviolet light (wavelength 365 nm), then heated at 170°C for 1 hour using a hot air circulation dryer, and cut into a size of 7 cm x 10 cm to prepare a measurement sample for the relative dielectric constant (Dk) and dielectric loss tangent (Df). The measurement sample obtained above was dried at 105°C for 10 minutes using a hot air circulation dryer, and then the relative permittivity (Dk) and dielectric loss tangent (Df) were measured in the 10 GHz band using a split post dielectric resonator method (SPDR method), and evaluated according to the following criteria. (Evaluation criteria for relative dielectric constant (Dk)) A: 2.8 or less B: More than 2.8~3.0 or less C: over 3.0 (Evaluation criteria for dielectric dissipation factor (Df)) A:0.0100 or less B: More than 0.0100~0.0120 or less C: over 0.0120

[0176] [Evaluation of via resolution] (1) Preparation of laminate for evaluation The copper foil surface of a printed wiring board substrate (Showa Denko Materials Co., Ltd., product name "MCL-E-679"), which had a copper foil (12 μm thick) laminated to a glass epoxy base, was pre-roughened with a pre-roughening solution (MEC Co., Ltd., product name "CZ-8100"), followed by rinsing with water and drying. Next, the carrier film on the second surface of the carrier film-attached photosensitive resin film produced in each example was peeled off and removed, so that the exposed second surface became the bonding surface, and the film was laminated onto the copper foil of the pre-roughened printed wiring board substrate. Lamination was performed using a press-type vacuum laminator (Meiki Seisakusho Co., Ltd., product name "MVLP-500") under the following conditions: press hot plate temperature 70°C, vacuum time 20 seconds, lamination press time 30 seconds, atmospheric pressure 4 kPa or less, and pressure 0.4 MPa. After lamination, the laminate was left at room temperature for at least 1 hour to obtain a laminate for evaluation in which a photosensitive resin film and a carrier film were laminated in this order on the copper foil surface of the substrate for printed wiring board. (2) Sensitivity measurement A 41-step tablet was placed on the carrier film of the evaluation laminate obtained above. Next, exposure was performed using a direct imaging exposure device (manufactured by Oak Manufacturing Co., Ltd., product name "DXP-3512") using an ultra-high pressure mercury lamp as a light source. The exposure pattern used was a dot pattern in which dots ranging from φ30 to 100 μm were arranged in a grid pattern. After exposure, the laminate was left to stand at room temperature for 30 minutes, after which the carrier film on the first surface side of the evaluation laminate obtained above was removed, and the unexposed photosensitive resin film was spray-developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 30°C. After development, the amount of exposure energy at which the gloss remaining step number of the 41-step tablet became 4.0 was determined as the sensitivity of the photosensitive resin film (unit: mJ / cm). 2 The pattern exposed at this sensitivity was evaluated according to the following criteria. (3) Evaluation of via resolution The via resolution was evaluated using an optical microscope by exposing a via pattern formed by exposure and spray development at an exposure energy amount corresponding to the sensitivity of the photosensitive resin film determined in (2) above, and then evaluating the pattern according to the following criteria. (Evaluation criteria) A: The φ60 μm via part of the dot pattern is open. C: The φ60 μm via portion of the dot pattern is not open.

[0177] [Evaluation of adhesive strength with plated copper] (1) Preparation of laminate for evaluation and measurement of sensitivity of photosensitive resin film The same procedures as in (1) and (2) of [Evaluation of via resolution] above were carried out to prepare a laminate for evaluation, except that the exposure machine used in the procedures in (1) and (2) of [Evaluation of via resolution] above was changed to a parallel light exposure machine using an ultra-high pressure mercury lamp as the light source (manufactured by ORC Manufacturing Co., Ltd., product name "EXM-1201"), and the amount of exposure energy at which the gloss remaining step number was 8.0 was determined. This was used as the sensitivity of the photosensitive resin film (unit: mJ / cm 2 ) was decided. (2) Exposure process and development process The carrier film on the first surface of the evaluation laminate was peeled off and the entire surface was exposed to light with the exposure energy amount corresponding to the sensitivity calculated above to cure the photosensitive resin film. After exposure, the laminate was left at room temperature for 30 minutes, and then the unexposed areas of the photosensitive resin film were spray-developed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 30°C. (3) Post-cure treatment Next, a UV conveyor device (manufactured by Oak Manufacturing Co., Ltd.) with a high-pressure mercury lamp was used to expose the film to 2 J / cm . 2 After that, the substrate was heated at 170°C for 1 hour using a hot air circulation dryer. (4) Roughening treatment The heated evaluation laminate was treated with a swelling solution "Swelling Dip Securigant P" at 70°C for 5 minutes, followed by a roughening treatment using a roughening solution "Dosing Securigant P500J" at 70°C for 10 minutes. Subsequently, a neutralization treatment was performed using a neutralizing solution "Reduction Conditioner Securigant P500" at 50°C for 5 minutes. After that, a hydrofluoric acid treatment was performed at room temperature for 10 minutes using buffered hydrofluoric acid "LAL1800 SA High-Purity Buffered Hydrofluoric Acid." The swelling solution, roughening solution, and neutralizing solution were all manufactured by Atotech Japan, and the buffered hydrofluoric acid was manufactured by Stella Chemifa Corporation. (5) Plating The evaluation laminate after the roughening treatment was subjected to electroless plating treatment at 30°C for 15 minutes using an electroless plating solution "Prigant MSK-DK" (manufactured by Atotech Japan Co., Ltd.). Then, electroplating treatment was performed at 24°C and 2 A / dm using an electroplating solution "Cupracid HL" (manufactured by Atotech Japan Co., Ltd.). 2 The plating was carried out for 1.5 hours to form a copper plated layer on the interlayer insulating layer, with the thickness of the copper plated being 25 μm. (6) Measurement of adhesive strength with plated copper The adhesive strength to plated copper was measured by perpendicular peel strength at 23°C in accordance with JIS C6481:1996 and evaluated according to the following criteria. (Evaluation criteria) A: More than 0.4kN / m B: More than 0.1kN / m~0.4kN / m or less C: 0.1kN / m or less

[0178] [Table 1]

[0179] [Table 2]

[0180] Details of each component listed in Tables 1 and 2 are as follows:

[0181] [Component (A)] Compound having a carboxyl group and an acryloyl group: Nippon Kayaku Co., Ltd., product name "ZXR-1807H", acid value: 110 mg KOH / g, weight average molecular weight (Mw): 2,000

[0182] [(B) Component] Biphenyl aralkyl epoxy resin: Nippon Kayaku Co., Ltd., product name "NC-3000-L", epoxy group equivalent: 272g / eq Naphthol-type epoxy resin: Nippon Steel & Sumitomo Metal Corporation, product name "ESN-475V", epoxy group equivalent: 325g / eq Maleimide resin: Aromatic bismaleimide resin with an indane skeleton Allyl resin: Diallyl isocyanurate compound, manufactured by Shikoku Chemicals Corporation, product name "LDAIC"

[0183] [(C) component] Photopolymerization initiator 1: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide Photopolymerization initiator 2: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone 1-(O-acetyloxime)

[0184] [(D) component] Silica 1: Admatechs Co., Ltd., product name "SC2050-MB", average particle diameter (D 50 ):0.5μm, true density 2,200kg / m 3 Silica 2: TAT Corporation, product name "BQQ-0710SCB", average particle size (D 50 ):0.7μm, true density 1,350kg / m 3

[0185] [(E) component] Polytetrafluoroethylene particles: Mitsubishi Pencil Co., Ltd., product name "MPT-N8", average particle diameter (D 50 ): 0.2~0.3μm

[0186] [Component (F)] Polybutadiene elastomer: butadiene-styrene random copolymer, manufactured by Cray Valley, product name "Ricon 100", number average molecular weight (Mn): 4,500 Acid anhydride-modified polybutadiene: Cray Valley Corporation, product name "Ricon 131MA17", number average molecular weight (Mn): 5,400, number of acid anhydride groups per molecule: 9

[0187] [(G) component] Organic peroxide: 1,3-di(t-butylperoxyisopropyl)benzene

[0188] [(H) component] Curing accelerator: 1-benzyl-2-phenylimidazole

[0189] [Component (I)] Sensitizer: 4,4'-bis-(diethylamino)benzophenone Polymerization inhibitor: 4-tert-butylpyrocatechol

[0190] As can be seen from Table 2, all of the cured products formed from the photosensitive resin films of Examples 1 to 7 of this embodiment had excellent dielectric properties and high conductor adhesion. [Explanation of symbols]

[0191] 100A multilayer printed wiring board 101 Substrate 102 Circuit Pattern 103 Photosensitive layer 104 Interlayer insulating layer 105 Beer 106 seed layer 107 Resist Pattern 108 copper circuit layers 109 Solder resist layer

Claims

1. A photosensitive resin film containing (A) a compound having an ethylenically unsaturated group, (B) a thermosetting resin, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a fluorine-containing resin, the photosensitive resin film has a first surface and a second surface opposite to the first surface; 2 J / cm ２ After irradiating with ultraviolet light, the resin is cured by heating at 170°C for 1 hour. The weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the first surface is exposed and the second surface is not exposed is a, When the weight loss amount when the roughening treatment is performed under the following roughening treatment conditions in a state where the second surface is exposed and the first surface is not exposed is defined as b, a is smaller than b and a is 10 g / m ２ is as follows: The photosensitive resin film has a total thickness of 2 to 110 μm. (Roughening treatment conditions) The object to be roughened is immersed in a swelling solution at 70°C (an aqueous solution containing Swelling Dip Securigant P manufactured by Atotech Japan Co., Ltd. at a concentration of 49.85% by mass and sodium hydroxide at 0.3% by mass) for 5 minutes, then immersed in an oxidizing agent solution at 80°C (an aqueous solution containing Dosing Securigant P500J manufactured by Atotech Japan Co., Ltd. at a concentration of 14.55% by mass and sodium hydroxide at 3.69% by mass) for 15 minutes, and further immersed in a neutralizing solution at 50°C (an aqueous solution containing Reduction Conditioner Securigant P500 manufactured by Atotech Japan Co., Ltd. at a concentration of 10.65% by mass and 95% sulfuric acid at 8.27% by mass) for 5 minutes, and then dried.

2. The photosensitive resin film according to claim 1 , wherein the compound (A) having an ethylenically unsaturated group is a compound having an ethylenically unsaturated group and an acidic substituent.

3. 2. The photosensitive resin film according to claim 1, wherein the (B) thermosetting resin is at least one selected from the group consisting of epoxy resins, maleimide resins, allyl resins, and vinyl resins.

4. 2. The photosensitive resin film according to claim 1, wherein the (D) inorganic filler contains silica, and the content of the silica is 2 to 60 mass %.

5. The (D) inorganic filler has a true density of 1,500 kg / m ３ The photosensitive resin film according to claim 1 , comprising silica having the following:

6. 2. The photosensitive resin film according to claim 1, wherein the content of the fluorine-containing resin (E) is 5 to 60 mass % based on the total amount of resin components of the photosensitive resin film.

7. The photosensitive resin film according to claim 1 , further comprising (F) an elastomer.

8. The photosensitive resin film according to claim 1 , wherein the first surface is a surface on which a circuit pattern is formed by copper plating, and the second surface is an attachment surface when laminating the photosensitive resin film.

9. The photosensitive resin film according to claim 1 , which is used to form an interlayer insulating layer having a photovia.

10. A printed wiring board having an interlayer insulating layer which is a cured product of the photosensitive resin film according to claim 1.

11. A semiconductor package comprising the printed wiring board according to claim 10.

12. A method for manufacturing a printed wiring board, comprising the following steps (1) to (4): (1): The photosensitive resin film according to any one of claims 1 to 9 is laminated onto one or both sides of a circuit board with the second surface serving as an attachment surface. (2) Forming an interlayer insulating layer having vias by exposing and developing the photosensitive resin film laminated in (1) above. (3) Heat-curing the interlayer insulating layer having the vias. (4) Forming a circuit pattern on the surface of the interlayer insulating layer opposite to the circuit board.

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