Photosensitive resin composition, photosensitive resin film, multilayer printed circuit board and semiconductor package, and method for manufacturing a multilayer printed circuit board.

Abstract

The present invention provides a photosensitive resin composition having excellent dielectric loss tangent (Df), a photosensitive resin film formed using the photosensitive resin composition, a multilayer printed circuit board and a method for manufacturing the same, and a semiconductor package. [Solution] A photosensitive resin composition containing (A) a compound having an acidic substituent and a (meth)acryloyl group, (B) a (meth)acrylate compound having two or more (meth)acryloyl groups, (C) a compound having two or more ethylenically unsaturated groups other than (meth)acryloyl groups, (D) a photopolymerization initiator, and (E) an organic peroxide; a photosensitive resin film formed using the photosensitive resin composition; a multilayer printed circuit board and a method for producing the same; and a semiconductor package.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a photosensitive resin film, a multilayer printed circuit board and a semiconductor package, and a method for manufacturing a multilayer printed circuit board. [Background technology]

[0002] In recent years, as electronic devices have become smaller and more high-performance, multilayer printed circuit boards (PCBs) have become more densely packed due to an increase in the number of circuit layers and miniaturization of wiring. In particular, the density of semiconductor package substrates such as BGAs (ball grid arrays) and CSPs (chip-size packages) on which semiconductor chips are mounted has become remarkable, and in addition to miniaturization of wiring, there is a demand for thinner interlayer insulating layers and smaller vias for interlayer connections.

[0003] A conventional method for manufacturing printed circuit boards is the build-up method (see, for example, Patent Document 1), in which interlayer insulating layers and conductive circuit layers are sequentially laminated to form a multilayer printed circuit board. In multilayer printed circuit boards, with the miniaturization of circuits, the semi-additive method, in which circuits are formed by plating, has become the mainstream. In conventional semi-additive manufacturing methods, for example, (1) a thermosetting resin film is laminated onto a conductor circuit, and the thermosetting resin film is heated and cured to form an interlayer insulating layer. (2) Next, vias for interlayer connection are formed by laser processing, and desmear treatment and roughening treatment are performed by alkaline permanganate treatment, etc. (3) After that, electroless copper plating is applied to the substrate, a pattern is formed using a resist, and then electrolytic copper plating is performed to form a copper circuit layer. (4) Subsequently, the resist is peeled off, and the circuit is formed by flash etching of the electroless layer.

[0004] As a method of forming vias in an interlayer insulating layer formed of a thermosetting resin film, laser processing is the mainstream, but the reduction of the via diameter by laser irradiation is approaching its limit. Further, in forming vias using a laser processing machine, it is necessary to form each via hole one by one. Therefore, when it is necessary to provide a large number of vias due to high density, there are problems that it takes a long time to form vias, the manufacturing cost is high, and the manufacturing efficiency is poor.

[0005] Under such circumstances, as a method capable of forming a large number of vias at once, a photosensitive resin composition containing an acid-modified vinyl group-containing epoxy resin, a photopolymerizable compound, a photopolymerization initiator, an inorganic filler, and a silane compound, and having an inorganic filler content of 10 to 80% by mass has been proposed to form a plurality of small-diameter vias at once by a photolithography method (see, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] By the way, in recent years, substrate materials are required to be applied to fifth-generation mobile communication systems (5G) antennas using radio waves in high-frequency bands and millimeter-wave radars using radio waves in the frequency band of 30 to 300 GHz. Therefore, improvement of dielectric properties for reducing transmission loss of high-frequency signals, that is, reduction of dielectric tangent, is required. However, the technology of Patent Document 2 did not satisfy such requirements.

[0008] In view of such a current situation, an object of the present embodiment is to provide a photosensitive resin composition having an excellent dielectric tangent (Df), a photosensitive resin film formed using the photosensitive resin composition, a multilayer printed wiring board and a manufacturing method thereof, and a semiconductor package.

Means for Solving the Problems

[0009] As a result of proceeding with studies to solve the above problems, the present inventors have found that the above problems can be solved by the following present embodiment. That is, the present embodiment relates to the following [1] to

[15] . [1] A compound having an acidic substituent and a (meth)acryloyl group, (B) A (meth)acrylate compound having two or more (meth)acryloyl groups, (C) A compound having two or more ethylenically unsaturated groups other than the (meth)acryloyl group, (D) A photopolymerization initiator, (E) An organic peroxide, A photosensitive resin composition containing. [2] The photosensitive resin composition according to [1] above, wherein the component (C) is a compound having at least one selected from the group consisting of a maleimide group, an allyl group, a nadimide group, and a vinyl group as an ethylenically unsaturated group other than the (meth)acryloyl group. [3] The photosensitive resin composition according to [1] above, wherein the component (C) is a compound having two or more maleimide groups. [4] The photosensitive resin composition according to [1] above, wherein the component (C) is a compound having two or more allyl groups. [5] The photosensitive resin composition according to [1] above, wherein the component (C) is a compound having two or more nadimide groups. [6] The photosensitive resin composition according to [1] above, wherein the component (C) is a compound having two or more vinyl groups. [7] Further, the photosensitive resin composition according to any one of [1] to [6] above, containing (F) an inorganic filler. [8] A photosensitive resin composition according to any one of [1] to [7] above, further comprising (G) a thiol compound. [9] A photosensitive resin composition according to any of [1] to [8] above, for use in forming photovias.

[10] The photosensitive resin composition according to any one of [1] to [9] above, wherein the dielectric loss tangent (Df) of the cured product at 10 GHz is 0.0040 to 0.0100.

[11] A photosensitive resin film formed using any of the photosensitive resin compositions described in [1] to

[10] above.

[12] The photosensitive resin film described in

[11] above, having a thickness of 1 to 100 μm.

[13] A multilayer printed circuit board comprising an interlayer insulating layer formed using the photosensitive resin composition described in any of [1] to

[10] above or the photosensitive resin film described in

[11] or

[12] above.

[14] A semiconductor package including the multilayer printed circuit board described in

[13] above.

[15] A method for manufacturing a multilayer printed circuit board, including (1) to (4) below. (1) Laminating the photosensitive resin film described in

[11] or

[12] above onto one or both sides of the circuit board. (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 interlayer insulating layer. [Effects of the Invention]

[0010] According to this embodiment, it is possible to provide a photosensitive resin composition having an excellent dielectric loss tangent (Df), a photosensitive resin film formed using the photosensitive resin composition, a multilayer printed circuit board and a method for manufacturing the same, and a semiconductor package. [Brief explanation of the drawing]

[0011] [Figure 1]This is a schematic diagram illustrating one aspect of the manufacturing process for a multilayer printed circuit board using the photosensitive resin film of this embodiment as the material for the interlayer insulating layer. [Modes for carrying out the invention]

[0012] In the numerical ranges described herein, the lower and upper limits of those ranges may be replaced with the values ​​shown in the examples. Furthermore, the lower and upper limits of a numerical range can be arbitrarily combined with the lower or upper limits of other numerical ranges. In the notation "AA~BB" for a numerical range, the numbers AA and BB at both ends are included in the range as the lower and upper limits, respectively.

[0013] In this specification, for example, the phrase "10 or more" means 10 and numbers greater than 10, and the same applies when the numbers are different. Similarly, for example, the phrase "10 or less" means 10 and numbers less than 10, and the same applies when the numbers are different.

[0014] In this specification, the content of each component in the photosensitive resin composition refers to the total content of multiple substances present in the photosensitive resin composition, unless otherwise specified, if there are multiple substances corresponding to each component.

[0015] In this specification, "ring-forming carbon number" refers to the number of carbon atoms required to form a ring, and does not include the number of carbon atoms in substituents on the ring. For example, both the cyclohexane skeleton and the methylcyclohexane skeleton have a ring-forming carbon number of 6.

[0016] The notation "(meth)acrylic XX" refers to either or both acrylic XX and its corresponding methacrylic XX. Similarly, "(meth)acryloyl group" refers to either or both an acryloyl group and a methacryloyl group.

[0017] In this specification, when the term "layer" is used, for example, as in "interlayer insulating layer," it includes not only solid layers, but also non-solid layers that are partially island-like, perforated, and layers where the interface with adjacent layers is unclear.

[0018] Furthermore, embodiments that arbitrarily combine the matters described herein are also included in this embodiment.

[0019] [Photosensitive resin composition] The photosensitive resin composition of this embodiment is (A) Compounds having an acidic substituent and a (meth)acryloyl group, (B) A (meth)acrylate compound having two or more (meth)acryloyl groups, (C) A compound having two or more ethylenically unsaturated groups other than a (meth)acryloyl group, (D) Photopolymerization initiator, (E) Organic peroxides and This is a photosensitive resin composition containing [a specific substance]. In this specification, each of the above components may be abbreviated as "(A) component," etc., as appropriate, and other components may also be abbreviated in the same manner.

[0020] <(A) Compounds having an acidic substituent and a (meth)acryloyl group> Component (A) is a compound having an acidic substituent and a (meth)acryloyl group. Component (A) is a compound having a (meth)acryloyl group and undergoing photoradical polymerization. (A) Component (A) may be used alone or in combination of two or more components.

[0021] Component (A) has an acidic substituent from the viewpoint of alkali developability. Examples of acidic substituents on component (A) include carboxyl groups, sulfonic acid groups, and phenolic hydroxyl groups. Among these, carboxyl groups are preferred from the viewpoint of alkali developability. (A) The acid value of component (A) is preferably 20 to 200 mg KOH / g, more preferably 50 to 160 mg KOH / g, and even more preferably 90 to 120 mg KOH / g, from the viewpoint of dielectric properties and alkali developability. The acid value of component (A) can be measured by the method described in the examples.

[0022] The weight-average molecular weight of component (A) is preferably 500 to 30,000, more preferably 700 to 10,000, and even more preferably 1,000 to 5,000, from the viewpoint of heat resistance and insulation reliability. In this specification, the weight-average molecular weight is the value obtained on a standard polystyrene basis by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent, and more specifically, the value measured according to the method described in the examples.

[0023] Component (A) preferably contains an alicyclic skeleton from the viewpoint of low dielectric constant and low dielectric loss tangent. (A) As for the alicyclic skeleton of component (A), from the viewpoint of resolution and dielectric properties, an alicyclic skeleton with 5 to 20 ring-forming carbon atoms is preferred, an alicyclic skeleton with 5 to 18 ring-forming carbon atoms is more preferred, an alicyclic skeleton with 6 to 16 ring-forming carbon atoms is even more preferred, an alicyclic skeleton with 7 to 14 ring-forming carbon atoms is particularly preferred, and an alicyclic skeleton with 8 to 12 ring-forming carbon atoms is most preferred.

[0024] The alicyclic skeleton of component (A) is preferably composed of two or more rings, more preferably of two to four rings, and even more preferably of three rings, from the viewpoint of resolution and dielectric properties. Examples of alicyclic skeletons with two or more rings include norbornane skeletons, decalin skeletons, bicycloundecane skeletons, and saturated dicyclopentadiene skeletons. Among these, saturated dicyclopentadiene skeletons are preferred from the viewpoint of resolution and dielectric properties. From a similar viewpoint, component (A) is preferably one that contains an alicyclic skeleton represented by the following general formula (A-1).

[0025] [ka] (wherein, R A1 represents an alkyl group having 1 to 12 carbon atoms and may be substituted at any position in the above alicyclic skeleton. m 1 is an integer of 0 to 6. * indicates a bonding site.)

[0026] In the above general formula (A-1), the alkyl group having 1 to 12 carbon atoms represented by R A1 includes, for example, 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, and the like. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is even more preferable. m 1 is an integer of 0 to 6, preferably an integer of 0 to 2, and more preferably 0. m 1 When it is an integer of 2 to 6, the plurality of R A1 may be the same or different from each other. Further, the plurality of R A1 may be substituted on the same carbon atom or on different carbon atoms within the possible range. * is a bonding site to another structure and may be bonded to any carbon atom on the alicyclic skeleton, but is preferably bonded to the carbon atom represented by 1 or 2 and the carbon atom represented by either 3 or 4 in the following general formula (A-1’).

[0027] [Chemical formula] (wherein, R A1 , m 1 and * are the same as those in the above general formula (A-1).)

[0028] Component (A) is preferably a compound obtained by reacting (a1) an epoxy resin modified with (a2) an organic acid containing a (meth)acryloyl group [hereinafter sometimes referred to as component (A')] with (a3) ​​a polybasic acid anhydride containing a saturated or unsaturated group (hereinafter also referred to as "acid-modified (meth)acryloyl group-containing epoxy resin derivative"). The following describes preferred embodiments of component (A) obtained from (a1) epoxy resin, (a2) (meth)acryloyl group-containing organic acid, and (a3) ​​saturated or unsaturated group-containing polybasic acid anhydride.

[0029] ((a1) Epoxy resin) (a1) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. (a1) Epoxy resin may be used alone or in combination of two or more types. (a1) Epoxy resins are classified into 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.

[0030] (a1) Epoxy resins can be classified into various types based on differences in their main skeleton, including epoxy resins with an alicyclic skeleton, novolac-type epoxy resins, bisphenol-type epoxy resins, aralkyl-type epoxy resins, and other epoxy resins. Among these, epoxy resins with an alicyclic skeleton and novolac-type epoxy resins are preferred.

[0031] -Epoxy resin with an alicyclic skeleton- The alicyclic skeleton of the epoxy resin having an alicyclic skeleton will be described in the same way as the alicyclic skeleton of component (A) described above, and the preferred embodiments will also be the same. As an epoxy resin having an alicyclic skeleton, epoxy resin represented by the following general formula (A-2) is preferred.

[0032] [ka] (In the formula, R A1 Each of these independently represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic skeleton. A2 Each of these independently represents an alkyl group having 1 to 12 carbon atoms. 1 is an integer from 0 to 6, m 2 n is an integer between 0 and 3. n is a number between 0 and 50.

[0033] In the above general formula (A-2), R A1 R in the above general formula (A-1) is A1 It is the same as, and the preferred form is also the same. In the above general formula (A-2), R A2 Examples of C1-C12 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups. C1-C6 alkyl groups are preferred, C1-C3 alkyl groups are more preferred, and methyl groups are even more preferred. In the above general formula (A-2), m 1 m in the above general formula (A-1) 1 It is the same as, and the preferred form is also the same. In the above general formula (A-2), m 2 is an integer between 0 and 3, preferably 0 or 1, and more preferably 0. In the general formula (A-2) above, n represents the number of structural units in parentheses and is a number between 0 and 50. Typically, epoxy resins are mixtures of structural units with different numbers in parentheses, so in that case, n is represented by the average value of the mixture. A number between 0 and 30 is preferred for n.

[0034] As the epoxy resin having an alicyclic skeleton, commercially available products may be used. Examples of commercially available products include "XD-1000" (manufactured by Nippon Kayaku Co., Ltd., product name) and "EPICLON® HP-7200" (manufactured by DIC Corporation, product name).

[0035] -Novolac-type epoxy resin- Examples of novolac-type epoxy resins include bisphenol novolac-type epoxy resins such as bisphenol A novolac-type epoxy resin, bisphenol F novolac-type epoxy resin, and bisphenol S novolac-type epoxy resin; phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, biphenyl novolac-type epoxy resin, and naphthol novolac-type epoxy resin. As the novolac-type epoxy resin, epoxy resin having a structural unit represented by the following general formula (A-3) is preferred.

[0036] [ka] (In the formula, R A3 Each of these independently represents either a hydrogen atom or a methyl group, Y A1 Each of these independently represents a hydrogen atom or a glycidyl group. A1 At least one of them is a glycidyl group.

[0037] R A3 From the viewpoint of resolution, it is preferable that both are hydrogen atoms. From a similar viewpoint, Y A1 Preferably, all of these are glycidyl groups. The number of structural units in the epoxy resin (a1) having the structural units represented by the above general formula (A-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, the adhesion strength to copper plating, heat resistance, and insulation reliability tend to improve. In the above general formula (A-3), R A3 Both are hydrogen atoms, Y A1 Those that all have a glycidyl group are sold as the "EXA-7376" series (manufactured by DIC Corporation, product name), and also R A3 Both are methyl groups, Y A1 All of these, which use a glycidyl group, are commercially available as the "EPON SU8" series (manufactured by Mitsubishi Chemical Corporation, product name).

[0038] Examples of bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and 3,3',5,5'-tetramethyl-4,4'-diglycidyloxydiphenylmethane. Examples of aralkyl epoxy resins include phenol aralkyl epoxy resins, biphenyl aralkyl epoxy resins, and naphthol aralkyl epoxy resins. Other epoxy resins include, for example, 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 chain epoxy resins, heterocyclic epoxy resins, spiro-ring-containing epoxy resins, and rubber-modified epoxy resins.

[0039] ((a2) Organic acid containing (meth)acryloyl group) (a2) As the (meth)acryloyl group-containing organic acid, a (meth)acryloyl group-containing monocarboxylic acid is preferred. Examples of (meth)acryloyl group-containing monocarboxylic acids include acrylic acid, acrylic acid dimers, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, α-cyanocinnamic acid, and other acrylic acid derivatives; semi-ester compounds which are reaction products of hydroxyl group-containing acrylates and dibasic acid anhydrides; and semi-ester compounds which are reaction products of (meth)acryloyl group-containing monoglycidyl ethers or (meth)acryloyl group-containing monoglycidyl esters and dibasic acid anhydrides. (a2) The component may be used alone or in combination of two or more components.

[0040] The semi-ester compounds are obtained by reacting one or more (meth)acryloyl group-containing compounds selected from the group consisting of hydroxyl group-containing acrylates, (meth)acryloyl group-containing monoglycidyl ethers, and (meth)acryloyl group-containing monoglycidyl esters with a dibasic acid anhydride. In this reaction, it is preferable to react the (meth)acryloyl group-containing compound and the dibasic acid anhydride in equimolar amounts.

[0041] Examples of hydroxyl group-containing acrylates used in the synthesis of semi-ester compounds include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, trimethylolpropanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Examples of vinyl group-containing monoglycidyl ethers include glycidyl (meth)acrylate.

[0042] The dibasic acid anhydride used in the synthesis of semi-ester compounds may contain saturated groups or unsaturated groups. Examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

[0043] In the reaction between component (a1) and component (a2), the amount of component (a2) used per equivalent of epoxy group of component (a1) is preferably 0.6 to 1.1 equivalents, more preferably 0.8 to 1.05 equivalents, and even more preferably 1.0 equivalent. By reacting component (a1) and component (a2) in the above ratio, the polymerizability of component (A) is improved, and the resolution of the resulting photosensitive resin composition tends to improve.

[0044] It is preferable to dissolve components (a1) and (a2) in an organic solvent and react them while heating. Furthermore, known reaction catalysts, polymerization inhibitors, etc., may be used during the reaction as needed.

[0045] Component (A'), obtained by reacting component (a1) and component (a2), has a hydroxyl group formed by a ring-opening addition reaction between the epoxy group of component (a1) and the carboxyl group of component (a2), when a (meth)acryloyl group-containing monocarboxylic acid is used as component (a2). Next, by further reacting component (a3) ​​with component (A'), an acid-modified (meth)acryloyl group-containing epoxy resin derivative can be obtained in which the hydroxyl group of component (A') (including the hydroxyl group originally present in component (a1)) and the acid anhydride group of component (a3) ​​are semi-esterified.

[0046] ((a3) Polybasic acid anhydrides) (a3) Component may contain saturated groups or unsaturated groups. Examples of (a3) ​​component 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. Component (a3) ​​may be used alone or in combination of two or more.

[0047] 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 adjusted by reacting 0.1 to 1.0 equivalents of component (a3) ​​with 1 equivalent of hydroxyl group in component (A').

[0048] The content of component (A) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoint of resolution and dielectric properties, it is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total amount of resin components in the photosensitive resin composition.

[0049] Herein, in this specification, "resin component" means resin and compounds that form resin through a curing reaction. For example, in the resin composition of this embodiment, components (A) to (E) are classified as resin components. If the resin composition of this embodiment contains, as an optional component, a resin or a compound that forms a resin by a curing reaction in addition to the above-mentioned components, these optional components are also included in the resin component. Examples of optional components corresponding to the resin component include (G) thiol compounds, (H) epoxy resins, (I) curing accelerators for epoxy resins, and (J) other components such as surface modifiers. On the other hand, (F) inorganic fillers and (J) pigments, flame retardants, etc. as other components shall not be included in the resin components.

[0050] <(B)(meth)acrylate compounds having two or more (meth)acryloyl groups> The photosensitive resin composition of this embodiment contains (B) a (meth)acrylate compound having two or more (meth)acryloyl groups. Component (B), like component (A), also has a (meth)acryloyl group and is therefore a compound that undergoes photoradical polymerization. Component (B) is mainly used as a crosslinking agent for component (A). The photosensitive resin composition of this embodiment, by containing component (B), tends to have an increased crosslinking density due to the photoradical polymerization reaction, resulting in improved resistance to alkaline developers, resolution, heat resistance, and weather resistance. (B) Component may be used alone or in combination of two or more types.

[0051] The number of (meth)acryloyl groups in component (B) is two or more, preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 7, from the viewpoint of resolution, heat resistance and dielectric properties. Component (B) may have functional groups other than the (meth)acryloyl group, but it is preferable that it does not have acidic substituents such as carboxyl groups, sulfonic acid groups, or phenolic hydroxyl groups.

[0052] (B) Components include, for example, 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; bifunctional (meth)acrylate compounds such as aromatic di(meth)acrylates such as 2,2-bis(4-(meth)acryloxypolyethoxypolypropoxyphenyl)propane and bisphenol A diglycidyl ether di(meth)acrylate; (meth)acrylate compounds having a skeleton derived from trimethylolpropane such as trimethylolpropane tri(meth)acrylate; and tetramethylolmethane such as tetramethylolmethane tri(meth)acrylate and tetramethylolmethane tetra(meth)acrylate. Examples include (meth)acrylate compounds having a skeleton derived from; (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; trifunctional or more (meth)acrylate compounds having a skeleton derived from diglycerin; and (meth)acrylate compounds having a skeleton derived from isocyanuric acid, such as isocyanuric acid EO-modified di and triacrylates and ε-caprolactone-modified tris(acryloxyethyl)isocyanurate. Here, the above-mentioned "(meth)acrylate compound having a skeleton derived from XXX" (where XXX is a compound name) refers to an esterified product of XXX and (meth)acrylic acid, and this esterified product also includes compounds modified with alkylene oxy groups.

[0053] Among the above, component (B) is preferably a (meth)acrylate compound having a skeleton derived from trimethylolpropane (hereinafter also referred to as "component (B1)") or a (meth)acrylate compound having a skeleton derived from dipentaerythritol (hereinafter also referred to as "component (B2)"), from the viewpoint of resolution, heat resistance and dielectric properties, and it is more preferable to use these in combination. If component (B) contains component (B1) and component (B2), the content ratio of the two [(B1) component:(B2) component] is preferably 1:99 to 40:60 by mass, more preferably 3:97 to 20:80, and even more preferably 5:95 to 15:85. (B1) Trimethylolpropane tri(meth)acrylate is preferred as component (B2).

[0054] The content of component (B) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoint of resolution, heat resistance and dielectric properties, it is preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 30 to 50 parts by mass, per 100 parts by mass of component (A).

[0055] <(C) Compounds having two or more ethylenically unsaturated groups other than (meth)acryloyl groups> The photosensitive resin composition of this embodiment contains a compound having two or more ethylenically unsaturated groups other than (C)(meth)acryloyl groups. Component (C) is a compound that undergoes a thermal radical polymerization reaction using the organic peroxide (E), described later, as a polymerization initiator, and mainly contributes to improving the heat resistance of the cured product of the photosensitive resin composition of this embodiment. Since component (C) can be cured without generating hydroxyl groups like epoxy resins, the photosensitive resin composition of this embodiment containing component (C) tends to have excellent dielectric loss tangent (Df). (C) Component may be used alone or in combination of two or more types.

[0056] In this specification, "ethylenically unsaturated group" means a substituent containing an ethylenically unsaturated bond. Furthermore, "ethylenically unsaturated bond" means a carbon-carbon double bond capable of addition reactions, and does not include double bonds in aromatic rings. Examples of ethylenically unsaturated groups other than the (meth)acryloyl group include maleimide, nadiimide, allyl, vinyl, propargyl, butenyl, ethynyl, and phenylethynyl groups. Among these, one or more selected from the group consisting of maleimide, allyl, nadiimide, and vinyl groups are preferred. Component (C) may have functional groups other than the ethylenically unsaturated group described above, but it is preferable that it does not have acidic substituents such as carboxyl groups, sulfonic acid groups, or phenolic hydroxyl groups; or (meth)acryloyl groups.

[0057] Component (C) is preferably one or more selected from the group consisting of compounds having two or more maleimide groups (hereinafter also referred to as "(C1) polyfunctional maleimide compounds"), compounds having two or more allyl groups (hereinafter also referred to as "(C2) polyfunctional allyl compounds"), compounds having two or more nadiimide groups (hereinafter also referred to as "(C3) polyfunctional nadiimide compounds"), and compounds having two or more vinyl groups (hereinafter also referred to as "(C4) polyfunctional vinyl compounds"). The following explains these ingredients in order.

[0058] ((C1) polyfunctional maleimide compound) (C1) The polyfunctional maleimide compound has two or more maleimide groups, preferably 2 to 6, more preferably 2 to 5, and even more preferably 2 to 4, from the viewpoint of heat resistance and handling. (C1) Examples of polyfunctional maleimide compounds include aromatic maleimide compounds and aliphatic maleimide compounds. Among these, aromatic maleimide compounds are preferred from the viewpoint of heat resistance and ease of handling. In this specification, "aromatic maleimide compound" means a compound having an N-substituted maleimide group directly bonded to an aromatic ring, and "aliphatic maleimide compound" means a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0059] Examples of aromatic maleimide compounds include N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl- 4,4'-Diphenylmethanebismaleimide, bis(4-maleimidophenyl) ether, bis(4-maleimidophenyl) sulfone, bis(4-maleimidophenyl) sulfide, bis(4-maleimidophenyl) ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-male (imidophenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4-bis(3-maleimidophenoxy)biphenyl, 4,4-Bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, bis(4-maleimidophenoxy)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide Hoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl ]benzene, 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis Examples include bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide, and biphenyl aralkyl maleimide resins. Among these, biphenyl aralkyl maleimide resins are preferred.

[0060] ((C2) polyfunctional allyl compounds) (C2) The polyfunctional allyl compound has two or more allyl groups, preferably 2 to 6, more preferably 2 to 5, and even more preferably 2 to 4, from the viewpoint of heat resistance and handling. (C2) As the polyfunctional allyl compound, polyfunctional allyl compounds having a heterocycle are preferred. Examples of polyfunctional allyl compounds having heterocyclic rings include allyl group-containing isocyanurates such as diallyl isocyanurate and triallyl isocyanurate; allyl group-containing cyanurates such as diallyl cyanurate and triallyl cyanurate; and 1,3,4,6-tetraallyl glycoluryl. Among these, allyl group-containing isocyanurates are preferred from the viewpoint of heat resistance, dielectric properties, and ease of handling, and diallyl isocyanurate is more preferred.

[0061] Examples of allyl compounds other than polyfunctional allyl compounds having heterocyclic rings include allyl ether compounds such as trimethylolpropane trialyl ether, pentaerythritol diallyl ether, pentaerythritol trialyl ether, pentaerythritol tetraallyl ether, bisphenol A diallyl ether, bisphenol F diallyl ether, propylene glycol diallyl ether, glycerin diallyl ether, and polyoxypropylene diallyl ether; and allyl ester compounds such as diallyl phthalate, ethylene glycol bisallyl carbonate, diallyl naphthalate, and trimellitic acid trialyl.

[0062] ((C3) polyfunctional nadiimide compound) (C3) As a polyfunctional nadiimide compound, a bisallyl nadiimide compound represented by the following general formula (C-1) is preferred.

[0063] [ka] (In the formula, X C1 This represents a divalent organic group with 1 to 20 carbon atoms.

[0064] X C1 Examples of divalent organic groups having 1 to 20 carbon atoms, represented by , include alkylene groups, alkenylene groups, alkynylene groups, arylene groups, or divalent linking groups formed by combinations of these. Examples of alkylene groups include methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, and 1,5-pentamethylene group. Examples of alkenylene groups include vinylene, propenylene, and butenylene groups. Examples of alkylylene groups include ethynylene groups and propynylene groups. Examples of arylene groups include phenylene groups and naphthylene groups. X C1 Among these, alkylene groups or arylene groups are preferred. X C1 The number of carbon atoms in the divalent organic group having 1 to 20 carbon atoms, represented by , is preferably 2 to 18, more preferably 4 to 16, and even more preferably 6 to 14.

[0065] Also, X C1 From the viewpoint of dielectric properties, it is preferable that the organic group is a divalent organic group represented by the following general formula (C-2) or a divalent organic group represented by the following general formula (C-3), and more preferably a divalent organic group represented by the following general formula (C-3).

[0066] [ka] (X C2 , X C3 and X C4 Each of these is an alkylene group having 1 to 10 carbon atoms. (* indicates a bonding site.)

[0067] X C2 , X C3 and X C4 The alkylene group with 1 to 10 carbon atoms represented by X C1 The same examples as those given in the explanation can be cited. Among these, the methylene group is preferred. X C2 , X C3 and X C4The number of carbon atoms in the alkylene group having 1 to 10 carbon atoms, represented by , is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1.

[0068] ((C4) polyfunctional vinyl compound) Examples of (C4) polyfunctional vinyl compounds include m-divinylbenzene, p-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 2,3-divinylnaphthalene, 2,7-divinylnaphthalene, 2,6-divinylnaphthalene, 4,4'-divinylbiphenyl, 4,3'-divinylbiphenyl, 4,2'-divinylbiphenyl, 3,2'-divinylbiphenyl, 3,3'-divinylbiphenyl, and 2,2'- Examples include compounds having vinyl groups directly bonded to aromatic rings, such as divinylbiphenyl, 2,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributylnaphthalene, and 2,2'-divinyl-4-ethyl-4'-propylbiphenyl; vinyl ether compounds such as 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, and diethylene glycol divinyl ether; and polymers having vinyl groups, such as polybutadiene elastomers having 1,2-vinyl groups and polyisoprene elastomers having 1,2-vinyl groups. Among these, polymers having vinyl groups are preferred, and polybutadiene-based elastomers having 1,2-vinyl groups are more preferred. The 1,2-vinyl groups in polybutadiene-based elastomers having 1,2-vinyl groups are vinyl groups contained in the butadiene-derived structural unit represented by the following formula (C-4).

[0069] [ka]

[0070] The polybutadiene elastomer having 1,2-vinyl groups may be a polybutadiene homopolymer having 1,2-vinyl groups, or a copolymer of butadiene and a monomer other than butadiene. As the copolymer of butadiene and a monomer other than butadiene, a butadiene-styrene copolymer having 1,2-vinyl groups is preferred.

[0071] The content of structural units having 1,2-vinyl groups (hereinafter also referred to as "vinyl group content") relative to the total structural units constituting the polybutadiene-based elastomer having 1,2-vinyl groups is not particularly limited, but is preferably 10 to 98 mol%, more preferably 20 to 95 mol%, and even more preferably 25 to 90 mol%.

[0072] Butadiene-styrene copolymers having 1,2-vinyl groups are commercially available, such as "Ricon® 100," "Ricon® 181," and "Ricon® 184" (all manufactured by Clay Valley, trade names).

[0073] Furthermore, polybutadiene elastomers having 1,2-vinyl groups may also have acid anhydride groups from the viewpoint of resolution. Examples of acid anhydride groups include acid anhydride groups derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc., with acid anhydride groups derived from maleic anhydride being preferred. When a polybutadiene-based elastomer having 1,2-vinyl groups also has acid anhydride groups, the number of acid anhydride groups in one molecule is preferably 1 to 12, more preferably 3 to 11, and even more preferably 6 to 10, from the viewpoint of resolution and dielectric properties.

[0074] Polybutadiene elastomers having acid anhydride groups derived from maleic anhydride are commercially available, such as "POLYVEST(registered trademark) MA75" and "POLYVEST(registered trademark) EP MA120" (both manufactured by Evonik, trade names), and "Ricon(registered trademark) 130MA8", "Ricon(registered trademark) 131MA5", "Ricon(registered trademark) 131MA17" and "Ricon(registered trademark) 184MA6" (all manufactured by Clay Valley, trade names).

[0075] The number-average molecular weight of the polybutadiene elastomer having 1,2-vinyl groups is not particularly limited, but from the viewpoint of resolution, impact resistance, and heat resistance, it is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and even more preferably 3,000 to 6,000. Herein, in this specification, the number-average molecular weight is the value obtained on a standard polystyrene basis by gel permeation chromatography (GPC) using tetrahydrofuran as the solvent, and more specifically, the value measured according to the method described in the examples.

[0076] The photosensitive resin composition of this embodiment preferably contains, as component (C), one or more selected from the group consisting of components (C1), (C2), and (C3), and component (C4), and more preferably contains, one or more selected from the group consisting of components (C1), (C2), and (C3), and a polybutadiene elastomer having a 1,2-vinyl group. When the photosensitive resin composition of this embodiment contains one or more components selected from the group consisting of (C1), (C2), and (C3), and a polybutadiene elastomer having 1,2-vinyl groups, the content ratio [one or more components selected from the group consisting of (C1), (C2), and (C3): polybutadiene elastomer having 1,2-vinyl groups] is preferably 40:60 to 95:5, more preferably 50:50 to 90:10, and even more preferably 60:40 to 85:15 by mass, from the viewpoint of resolution, heat resistance, and dielectric properties.

[0077] The content of component (C) in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoint of heat resistance and dielectric properties, it is preferably 1 to 80% by mass, more preferably 3 to 60% by mass, and even more preferably 6 to 50% by mass, based on the total amount of resin components in the photosensitive resin composition.

[0078] <(D) Photopolymerization initiator> (D) The photopolymerization initiator is mainly a polymerization initiator for the photoradical polymerization reaction of the (meth)acryloyl group present in component (A) and component (B). The photosensitive resin composition of this embodiment, by containing (D) a photopolymerization initiator, promotes the photoradical polymerization reaction of components (A) and (B), which tends to improve resolution, heat resistance, and dielectric properties. (D) The photopolymerization initiator may be used alone or in combination of two or more types.

[0079] (D) The photopolymerization initiator is not particularly limited as long as it can photopolymerize (meth)acryloyl groups, and can be appropriately selected from commonly used photopolymerization initiators. (D) Examples of photopolymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane, and N,N-dimethylaminoacetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 9-F Acridine compounds such as phenylacridine and 1,7-bis(9,9'-acridinyl)heptane; acylphosphine oxide compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone-1-(O-acetyl oxime) Examples include 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.

[0080] Among these, acetophenone compounds, thioxanthone compounds, and benzophenone compounds are preferred, and from the viewpoint of improving sensitivity and enhancing deep curing properties, it is even more preferable to use acetophenone compounds, thioxanthone compounds, and benzophenone compounds in combination. (D) The content of the acetophenone compound in the photopolymerization initiator is preferably 50 to 98% by mass, more preferably 70 to 95% by mass, and even more preferably 80 to 90% by mass. (D) The content of thioxanthone compounds or benzophenone compounds in the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 4 to 10% by mass, respectively. As the acetophenone compound, 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane is preferred. As the thioxanthone compound, 2,4-dimethylthioxanthone is preferred. As the benzophenone compound, 4,4'-bis(dimethylamino)benzophenone is preferred.

[0081] The content of (D) photopolymerization initiator in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoint of ensuring that the photoradical polymerization reaction proceeds homogeneously and sufficiently, it is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 2 to 4 parts by mass, based on 100 parts by mass of the total amount of component (A) and component (B).

[0082] <(E)Organic peroxide> (E) Organic peroxides are primarily polymerization initiators for the thermal radical polymerization reaction of the ethylenically unsaturated groups present in component (C). The photosensitive resin composition of this embodiment tends to have improved heat resistance and dielectric properties because the inclusion of (E) organic peroxide promotes the thermal radical polymerization reaction of component (C). (E) The organic peroxide is not particularly limited as long as it is an organic compound containing a peroxide bond (-OO-). (E) Organic peroxides may be used individually or in combination of two or more types.

[0083] (E) The 1-hour half-life temperature of the organic peroxide is not particularly limited, but from the viewpoint of suppressing unintended reactions before and during development, and then allowing the thermal radical polymerization reaction to proceed with appropriate heating, it is preferably 100 to 200°C, more preferably 120 to 170°C, and even more preferably 130 to 150°C. The 1-hour half-life temperature of (E) organic peroxide can be calculated by decomposing (E) organic peroxide in a solvent under multiple temperature conditions, determining the decomposition rate constant at each temperature, and then plotting these decomposition rate constants using an Arrhenius plot. In this embodiment, the 1-hour half-life temperature was measured under conditions of benzene and a concentration of (E) organic peroxide of 0.1 mol / L.

[0084] (E) 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-amyl peroxyisononanoate; t-butylcumyl peroxide and di-t-butyl Examples include peroxides, dialkyl peroxides such as dicumyl peroxide, di-t-hexyl peroxide, and 1,3-bis(2-t-butylperoxyisopropyl)benzene; peroxyesters such as t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butylperoxyisopropyl monocarbonate; peroxycarbonates such as t-butylperoxyisopropyl carbonate and polyethertetrakis(t-butylperoxycarbonate); and diacyl peroxides such as dibenzoyl peroxide. Among these, 1,3-bis(2-t-butylperoxyisopropyl)benzene is preferred.

[0085] The content of (E) organic peroxide in the photosensitive resin composition of this embodiment is not particularly limited, but from the viewpoint of ensuring that the thermal radical polymerization reaction proceeds homogeneously and sufficiently, it is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 12 parts by mass, per 100 parts by mass of component (C).

[0086] <(F) Inorganic filler> The photosensitive resin composition of this embodiment preferably further contains (F) an inorganic filler. The photosensitive resin composition of this embodiment tends to have improved heat resistance, flame retardancy, and low thermal expansion properties by containing (F) an inorganic filler. (F) The inorganic filler may be used alone or in combination of two or more types.

[0087] (F) Examples of inorganic fillers include silica, alumina, titania, tantalum oxide, zirconia, silicon nitride, barium titanate, barium carbonate, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, lead titanate, lead zirconate titanate, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum titanate, yttria-containing zirconia, barium silicate, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, zinc oxide, magnesium titanate, hydrotalcite, mica, calcined kaolin, and carbon. Among these, silica is preferred from the viewpoint of heat resistance, flame retardancy, and low thermal expansion. (F) The inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent.

[0088] (F) Volume average particle size of inorganic filler (D 50 From the viewpoint of resolution, the particle size is preferably 0.01 to 5 μm, more preferably 0.1 to 1 μm, and even more preferably 0.3 to 0.7 μm. (F) Volume average particle size of inorganic filler (D 50The particle size can be determined in accordance with the international standard ISO 13321 by measuring particles dispersed in a solvent with a refractive index of 1.38, and representing the particle size equivalent to 50% of the cumulative value (by volume) in the particle size distribution.

[0089] If the photosensitive resin composition of this embodiment contains (F) an inorganic filler, the content of (F) an inorganic filler is not particularly limited, but from the viewpoint of heat resistance, flame retardancy, low thermal expansion, and resolution, it is preferably 10 to 70% by mass, more preferably 30 to 65% by mass, and even more preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition. In this specification, "solid content" refers to the non-volatile content of the photosensitive resin composition, excluding volatile substances such as water and solvents. It means the components that remain without volatilizing when the photosensitive resin composition is dried, and includes liquid, syrup-like, and wax-like substances at room temperature around 25°C.

[0090] <(G) Thiol compounds> The photosensitive resin composition of this embodiment preferably further contains a (G) thiol compound. The photosensitive resin composition of this embodiment tends to suppress oxygen inhibition during photocuring due to the inclusion of a (G) thiol compound. As a result, even when the photosensitive resin composition of this embodiment is exposed to air after peeling off the carrier film, excellent surface curing properties are more easily obtained. Consequently, light scattering in the carrier film is suppressed, and excellent resolution is more easily obtained. (G) The thiol compound may be used alone or in combination of two or more types.

[0091] (G) The number of thiol groups in the thiol compound is not particularly limited, but is preferably two or more, more preferably two to eight, and even more preferably two to six. (G) Examples of thiol compounds include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate), pentaerythrityltetrathiol, and 2-ethyl-2-(sulfanylmethyl)propane-1,3-dithiol. Among these, pentaerythritol tetrakis(3-mercaptobutyrate) is preferred.

[0092] When the photosensitive resin composition of this embodiment contains a (G) thiol compound, the content of the (G) thiol compound is not particularly limited, but from the viewpoint of surface curability, it is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 1 to 12% by mass, based on the total amount of resin components of the photosensitive resin composition.

[0093] <(H) Epoxy resin> The photosensitive resin composition of this embodiment may further contain (H) epoxy resin. (H) Epoxy resin may be used alone or in combination of two or more types.

[0094] (H) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. (H) Epoxy resins are classified into 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.

[0095] (H) Epoxy resins are classified into various types based on differences in their main skeleton, and each type of epoxy resin is further classified as follows: Specifically, bisphenol-based epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; bisphenol-based novolac type epoxy resins such as bisphenol A novolac type epoxy resin and bisphenol F novolac type epoxy resin; novolac type epoxy resins other than the above bisphenol-based novolac type epoxy resins, such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, and biphenyl novolac type epoxy resin; phenol aralkyl type epoxy resin; stilbene type epoxy resin; naphtho Epoxy resins are classified into categories such as naphthalene skeleton-containing epoxy resins (e.g., lunovolac type epoxy resin, naphthol type epoxy resin, naphthol aralkyl type epoxy resin, naphthylene ether type epoxy resin); biphenyl type epoxy resin; biphenyl aralkyl type epoxy resin; xylylene type epoxy resin; dihydroanthracene type epoxy resin; alicyclic epoxy resins (e.g., saturated dicyclopentadiene type epoxy resin); heterocyclic epoxy resins; spiroring-containing epoxy resins; cyclohexanedimethanol type epoxy resin; trimethylol type epoxy resin; aliphatic chain epoxy resin; and rubber-modified epoxy resin. Among these, naphthalene skeleton-containing epoxy resins and biphenyl aralkyl type epoxy resins are preferred.

[0096] Whether or not the photosensitive resin composition of this embodiment contains (H) epoxy resin, and if so, the amount contained, can be appropriately determined according to the desired properties. For example, if the photosensitive resin composition of this embodiment contains (H) epoxy resin from the viewpoint of heat resistance and adhesion to copper wiring, the content of (H) epoxy resin may be 1 to 50% by mass, 5 to 40% by mass, or 10 to 30% by mass, based on the total amount of resin components of the photosensitive resin composition. On the other hand, the photosensitive resin composition of this embodiment may not contain (H) epoxy resin in order to reduce dielectric loss tangent. Even when (H) epoxy resin is included, the content of (H) epoxy resin may be 10% by mass or less, 5% by mass or less, or 1% by mass or less, based on the total amount of resin components of the photosensitive resin composition.

[0097] <(I) Curing accelerator for epoxy resins> If the photosensitive resin composition of this embodiment contains (H) epoxy resin, the photosensitive resin composition of this embodiment may further contain (I) a curing accelerator for epoxy resin. The photosensitive resin composition of this embodiment can improve the curability of the epoxy resin by (I) containing a curing accelerator for epoxy resins. (I) The epoxy resin curing accelerator may be used alone or in combination of two or more types.

[0098] (I) Examples of epoxy resin curing accelerators 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, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, isocyanate mask imidazole (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- Examples include tertiary amines such as ris(dimethylaminophenol), tetramethylguanidine, 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 hexadecyltributylphosnium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the above polybasic acid anhydrides; diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, and 2,4,6-triphenylthiopyrillium hexafluorophosphate. Among these, imidazole compounds are preferred from the viewpoint of curability, and 2-phenyl-1-benzyl-1H-imidazole is more preferred.

[0099] If the photosensitive resin composition of this embodiment contains (I) an epoxy resin curing accelerator, the amount of (I) the epoxy resin curing accelerator is not particularly limited, but from the viewpoint of ensuring that the thermosetting reaction proceeds homogeneously and sufficiently, it is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 2 to 4 parts by mass per 100 parts by mass of (H) epoxy resin. On the other hand, the photosensitive resin composition of this embodiment may not contain (I) an epoxy resin curing accelerator, for example, if it does not contain (H) an epoxy resin.

[0100] <(J) Other ingredients> The photosensitive resin composition of this embodiment may optionally contain other components as (J) other components. (J) Other components include, for example, resins other than those listed above; organic fillers; hardeners for epoxy resins; pigments such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, carbon black, and naphthalene black; adhesive aids such as melamine; foam stabilizers such as silicone compounds; polymerization inhibitors; thickeners; and flame retardants. Each of these may be used individually or in combination of two or more types. (J) The content of other components may be adjusted as appropriate according to their respective purposes, but each component may be 0.01 to 10% by mass, 0.05 to 5% by mass, or 0.1 to 1% by mass, based on the total amount of resin components in the photosensitive resin composition.

[0101] The photosensitive resin composition of this embodiment may contain a diluent as needed. Organic solvents can be used as diluents. Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ether compounds such as methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Diluents may be used individually or in combination of two or more. If the photosensitive resin composition of this embodiment contains a diluent, the concentration of the total solid content in the photosensitive resin composition is preferably 40 to 90% by mass, more preferably 50 to 85% by mass, and even more preferably 60 to 80% by mass.

[0102] The relative permittivity (Dk) of the cured product of the photosensitive resin composition of this embodiment at a frequency of 10 GHz is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 3.2 or less, more preferably 3.0 or less, and even more preferably 2.9 or less. The smaller the relative permittivity (Dk) of the cured product, the better, and there is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 2.3 or more, 2.4 or more, or 2.5 or more. The conditions for obtaining a cured product from the resin composition of this embodiment can be those described in the examples. The dielectric loss tangent (Df) can be measured by the method described in the examples.

[0103] The dielectric loss tangent (Df) of the cured product of the photosensitive resin composition of this embodiment at a frequency of 10 GHz is not particularly limited, but from the viewpoint of low transmission loss, it is preferably 0.0100 or less, more preferably 0.0090 or less, even more preferably 0.0080 or less, and particularly preferably 0.0070 or less. The smaller the dielectric loss tangent (Df) of the cured product, the better, and there is no particular limit to its lower limit, but considering the balance with other physical properties, it may be, for example, 0.0040 or more, 0.0045 or more, or 0.0050 or more. The conditions for obtaining a cured product from the resin composition of this embodiment can be those described in the examples. The dielectric loss tangent (Df) can be measured by the method described in the examples.

[0104] The photosensitive resin composition of this embodiment can be manufactured by mixing the above-mentioned components. For mixing, for example, a roll mill, bead mill, planetary mixer, or orbital mixer can be used.

[0105] The photosensitive resin composition of this embodiment is suitable for via formation by photolithography. Therefore, the photosensitive resin composition of this embodiment is suitable as a photosensitive resin composition for photovia formation. Furthermore, the photosensitive resin composition of this embodiment is suitable as a negative-type photosensitive resin composition.

[0106] [Photosensitive resin film] The photosensitive resin film of this embodiment is a photosensitive resin film formed using the photosensitive resin composition of this embodiment. The photosensitive resin film of this embodiment has excellent dielectric properties and is therefore suitable for forming interlayer insulating layers in multilayer printed circuit boards. The photosensitive resin film of this embodiment may have a carrier film on one side, and may also have a protective film on the other side.

[0107] Examples of carrier film materials include polyesters such as polyethylene terephthalate and polybutylene terephthalate; and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film is preferably 5 to 100 μm, more preferably 10 to 60 μm, and even more preferably 15 to 45 μm. Examples of protective films include films having the same material as the carrier film.

[0108] The photosensitive resin film of this embodiment can be manufactured, for example, by applying the photosensitive resin composition of this embodiment onto a carrier film and drying it as necessary. Examples of coating equipment include comma coaters, bar coaters, kiss coaters, roll coaters, gravure coaters, and die coaters. The drying temperature when drying the coating film formed by applying the photosensitive resin composition is preferably 60 to 150°C, more preferably 70 to 120°C, and even more preferably 80 to 100°C. The drying time is preferably 1 to 60 minutes, more preferably 2 to 30 minutes, and even more preferably 5 to 20 minutes.

[0109] The thickness of the photosensitive resin film is not particularly limited, but from the viewpoint of handling ease and thinning of multilayer printed circuit boards, it is preferably 1 to 100 μm, more preferably 3 to 50 μm, and even more preferably 5 to 40 μm.

[0110] [Multilayer printed circuit board and method for manufacturing the same] The multilayer printed circuit board of this embodiment includes an interlayer insulating layer formed using the photosensitive resin composition or photosensitive resin film of this embodiment. Furthermore, the "interlayer insulating layer" included in the multilayer printed circuit board of this embodiment also includes the layer after various processing or treatments such as the formation of vias and wiring, and roughening treatments have been performed. The method for manufacturing the multilayer printed circuit board of this embodiment is not particularly limited as long as it uses the photosensitive resin composition or photosensitive resin film of this embodiment, but the method for manufacturing the multilayer printed circuit board of this embodiment described below is preferred.

[0111] The method for manufacturing a multilayer printed circuit board according to this embodiment is a method for manufacturing a multilayer printed circuit board that includes the following (1) to (4). (1): Laminating the photosensitive resin film of this embodiment to one or both sides of the circuit board (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 "photovia formation step (2)"). (3) Heat-curing the interlayer insulating layer having vias (hereinafter also referred to as "heat treatment step (3)"). (4) Forming a circuit pattern on the interlayer insulating layer (hereinafter also referred to as "circuit pattern formation step (4)"). The manufacturing method of the multilayer printed circuit board according to this embodiment will be described below, with reference to Figure 1 as appropriate. In this specification, for convenience, certain operations may be referred to as "Step XX," but "Step XX" is not limited to the embodiments specifically described herein.

[0112] (Lamination process (1)) In the lamination process (1), the photosensitive resin film of this embodiment is laminated to one or both sides of the circuit board. Figure 1(a) illustrates the 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 to both sides of the substrate 101. Lamination can be performed by removing the protective film if the photosensitive resin film has one, then placing the photosensitive resin film on the substrate 101 side and pressing it down using a vacuum laminator or the like while applying pressure and heat. Lamination conditions can be, for example, a bonding temperature of 70-130°C, a bonding pressure of 0.1-1.0 MPa, and reduced pressure of 20 mmHg (26.7 hPa) or less. The lamination method can be either batch-based or continuous-roll lamination. If a carrier film is attached to the photosensitive layer 103 after lamination, the carrier film may be peeled off before exposure as described later, or it may be peeled off after exposure.

[0113] (Photovia formation process (2)) In the photovia formation step (2), the photosensitive layer formed in the lamination step (1) is exposed and developed to form an interlayer insulating layer having vias. Figure 1(b) illustrates the process of forming an interlayer insulating layer 104 having vias 105 by exposing and developing a photosensitive layer 103. By exposing the photosensitive layer 103 to light, a photoradical polymerization reaction is initiated by the (D) photopolymerization initiator contained in the photosensitive resin composition of this embodiment, thereby curing components (A) and (B).

[0114] The method for exposing the photosensitive layer 103 may be, for example, a mask exposure method in which active light is irradiated in an image pattern through a negative or positive mask pattern called artwork, or a direct drawing exposure method such as LDI (Laser Direct Imaging) exposure or DLP (Digital Light Processing) exposure, in which active light is irradiated in an image pattern. Examples of known light sources for active light include gas lasers such as carbon arc lamps, mercury vapor arc lamps, high-pressure mercury lamps, xenon lamps, and argon lasers; solid-state lasers such as YAG lasers; and semiconductor lasers that effectively emit ultraviolet or visible light. The exposure dose can be adjusted as appropriate depending on the light source used and the thickness of the photosensitive layer. For example, when exposing a photosensitive layer with a thickness of 1 to 100 μm using ultraviolet irradiation from a high-pressure mercury lamp, the exposure dose is preferably 10 to 1,000 mJ / cm². 2 More preferably 50-700 mJ / cm² 2 More preferably 150-400 mJ / cm² 2 That is the case.

[0115] Next, if a carrier film is present on the photosensitive layer 103, the carrier film is removed before development. During development, the uncured portion of the photosensitive layer 103 is removed, and the photocured portion is formed on the substrate as an interlayer insulating layer 104. The development method may be either wet development or dry development, but wet development is preferred. Examples of wet development methods include the dip method, battle method, spray method, brushing, slapping, scraping, and agitation immersion. Among these, the spray method is preferred from the viewpoint of improving resolution. Examples of developing solutions include alkaline aqueous solutions, aqueous developing solutions, and organic solvent developing solutions, with alkaline aqueous solutions being preferred among these. After exposure and development, post-exposure may be performed to enhance the degree of hardening of the interlayer insulating layer. The exposure amount in post-exposure is preferably 0.2 to 10 J / cm². 2, more preferably 0.5~5J / cm 2 That is the case.

[0116] There are no particular restrictions on the shape of a via. In terms of cross-sectional shape, examples include a square or an inverted trapezoid (a shape where the top side is longer than the bottom side). Note that an inverted trapezoid is a shape where the top side is longer than the bottom side. In terms of shape in plan view (the direction in which the bottom of the via is visible), examples include a circle or a square. In the photolithography method for forming vias in this embodiment, vias with an inverted trapezoidal cross-sectional shape can be formed. Vias having this shape are preferable because they have high adhesion of copper plating to the via wall surface. In the photolithography method for forming vias in this embodiment, the diameter of the vias can be made smaller than the diameter of vias produced 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 limit to the lower limit of the via diameter, but for example, it may be 15 μm or more, or 20 μm or more.

[0117] (Heat treatment process (3)) In the heat treatment step (3), the interlayer insulating layer having vias is heat-cured. In other words, in the heat treatment step (3), heating initiates a thermal radical polymerization reaction by (E) organic peroxide contained in the photosensitive resin composition of this embodiment, and, if (H) epoxy resin and (I) epoxy resin curing accelerator are included, an epoxy polymerization reaction by (I) epoxy resin curing accelerator, thereby heating and curing components (C) and (H). 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.

[0118] (Circuit pattern formation process (4)) In the circuit pattern formation step (4), a circuit pattern is formed on the interlayer insulating layer. From the viewpoint of forming fine wiring, the circuit pattern is preferably formed by a semi-additive process. The semi-additive process forms the circuit pattern and simultaneously conducts vias. Specifically, the semi-additive process preferably involves roughening, forming a seed layer, forming a resist pattern, forming a copper circuit layer, and removing the resist pattern in this order.

[0119] [Roughening treatment] The roughening treatment is a process that roughens the surface of the interlayer insulating layer to form anchors for irregularities. If smearing occurs in the photovia formation process (2), the roughening treatment and removal of the smear may be performed simultaneously using a roughening solution. Examples of cruder solutions include alkaline permanganate cruder solutions such as sodium permanganate cruder solution; chromium / sulfuric acid cruder solutions; and sodium fluoride / chromium / sulfuric acid cruder solutions.

[0120] [Formation of the seed layer] Figure 1(c) illustrates the process of forming the 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 electroless copper plating using a palladium catalyst or the like on the via bottom, via wall surface, and the entire surface of the interlayer insulating layer. The thickness of the seed layer 106 is not particularly limited, but may be, for example, 0.1 to 5 μm or 0.2 to 2 μm. A known electroless plating method can be applied. Commercially available electroless copper plating solutions can be used, such as "MSK-DK" from Attec Japan Co., Ltd. and the "Surupap® PEA" series from Uemura Kogyo Co., Ltd.

[0121] [Formation of resist pattern] Figure 1(d) illustrates the process of forming a resist pattern 107 on the seed layer 106. The resist pattern 107 can be formed, for example, by heat-pressing a dry film resist onto the seed layer 106 using a roll laminator or the like, and then exposing and developing it. The thickness of the dry film resist is not particularly limited, but is preferably 3 to 50 μm, and more preferably 5 to 30 μm. Commercially available dry film resists can be used, such as the "FOTECH®" series manufactured by Showa Denko Materials Co., Ltd.

[0122] The dry film resist can be exposed by passing it through a mask on which the desired wiring pattern is drawn. The exposure method can be the same as that used to form vias on a photosensitive resin film. After exposure, the dry film resist is developed using an alkaline aqueous solution to remove unexposed areas and form the resist pattern 107. Subsequently, plasma treatment may be performed to remove any development residue of the dry film resist, if necessary.

[0123] [Formation of copper circuit layers and removal of resist patterns] Figure 1(e) illustrates the process of forming the copper circuit layer 108. The copper circuit layer 108 is preferably formed by electrolytic copper plating. For electrolytic copper plating, commercially available electrolytic copper plating solutions, such as those containing copper sulfate, can be used. After electrolytic copper plating, the resist pattern 107 is removed using an alkaline aqueous solution or an amine-based stripping agent. Furthermore, flash etching to remove the seed layer 106 between wirings, removal of the palladium catalyst, etc., are performed as appropriate by known methods. In addition, if necessary, a post-bake treatment may be performed to sufficiently heat-cur any unreacted thermosetting components.

[0124] Figure 1(f) shows a multilayer printed circuit board 100A that is formed by repeating the above steps and has a solder resist layer 109 on its outermost surface. The solder resist layer 109 can be formed using a known photosensitive resin composition for solder resists.

[0125] The above describes a method for manufacturing a multilayer printed circuit board using the photosensitive resin composition of this embodiment to form vias. However, since the photosensitive resin composition of this embodiment has excellent pattern resolution, it is also suitable for forming cavities for embedding chips or passive elements, for example. The cavities can be suitably formed, for example, in the description of the multilayer printed circuit board above, by making the drawing pattern when exposing the photosensitive resin film to form a pattern such that the desired cavity can be formed.

[0126] [Semiconductor Packages] The semiconductor package of this embodiment is a semiconductor package that includes the multilayer printed circuit board of this embodiment. The semiconductor package of this embodiment can be manufactured by mounting semiconductor elements such as semiconductor chips and memory at predetermined positions on the multilayer printed circuit board of this embodiment, and then sealing the semiconductor elements with a sealing resin or the like. [Examples]

[0127] The embodiments will be described in more detail below with reference to examples, but the embodiments are not limited to these examples.

[0128] <Method for measuring acid value> The acid value of component (A) was calculated from the amount of potassium hydroxide solution required to neutralize component (A).

[0129] <Method for measuring weight-average molecular weight and number-average molecular weight> The weight-average molecular weight and number-average molecular weight were measured using the GPC measuring device and measurement conditions described below, and then converted using a calibration curve for standard polystyrene. The calibration curve was created using five sample sets of standard polystyrene ("PStQuick MP-H" and "PStQuick B," manufactured by Tosoh Corporation). (GPC measurement device) GPC system: High-speed GPC system "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Tosoh Corporation. Column: TSKgel SuperMultipore HZ-H column (column length: 15cm, column inner diameter: 4.6mm), manufactured by Tosoh Corporation. (Measurement conditions) Solvent: Tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 0.35ml / min Sample concentration: 10 mg / THF 5 ml Injection volume: 20μl

[0130] [1. Evaluation of relative permittivity (Dk) and dielectric loss tangent (Df)] Two protective films were prepared by peeling off the protective films from the carrier films and photosensitive resin films manufactured in each example and comparative example, and the photosensitive resin films were bonded together. Then, with the carrier films still attached to both sides, they were exposed to light at 400 mJ / cm² using a flatbed exposure machine. 2 (Wavelength 365nm) exposure was performed. Subsequently, the carrier films on both sides were peeled off and exposed to UV conveyor type exposure at 2 J / cm². 2 The material was irradiated with light at a wavelength of 365 nm. After heat treatment at 170°C for 1 hour in a hot air circulating dryer, it was cut into 7 cm x 10 cm pieces and used as the evaluation sample. The obtained evaluation samples were dried in a hot air circulating dryer at 105°C for 10 minutes, and the relative permittivity (Dk) and dielectric loss tangent (Df) were measured in the 10 GHz band using the split post dielectric resonator method (SPDR method).

[0131] [2. Evaluation of surface hardening properties] The protective film was peeled off from the carrier film and the photosensitive resin film with protective film manufactured in each example and comparative example. The photosensitive resin film was then laminated onto a 1.0 mm thick copper-clad laminate substrate using the resin film as the bonding surface to obtain a laminate with carrier film. The lamination was performed using a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., product name "MVLP-500") under the following conditions: pressing pressure of 0.4 MPa, press hot plate temperature of 70-80°C, vacuuming time of 25 seconds, lamination press time of 25 seconds, and atmospheric pressure of 4 kPa or less. Furthermore, a laminate with a carrier film was prepared using the same procedure as described above, and a laminate was obtained by peeling off and removing the carrier film from the laminate. The following exposure procedures were performed using the laminates with and without the carrier film obtained above. (1) Exposure conditions with carrier film For the laminate with a carrier film, a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd., product name "EXM-1201") using an ultra-high pressure mercury lamp as the light source is applied from the carrier film side at a pressure of 500 mJ / cm². 2 The laminate was fully exposed to light to cure the photosensitive resin film. Then, the carrier film was peeled off the laminate, and the resin surface appearance was observed after development using a 1% sodium carbonate aqueous solution at a spray pressure of 0.2 MPa for 60 seconds. (2) Exposure conditions without carrier film The laminate, from which the carrier film had been removed, was fully exposed from the photosensitive resin film side under the same conditions as above. After development using a 1% sodium carbonate aqueous solution at a spray pressure of 0.2 MPa for 60 seconds, the surface appearance of the resin was observed. The surface of the cured photosensitive resin film formed under the exposure conditions described in (1) and (2) above was visually observed and evaluated according to the following evaluation criteria. A: The hardened surface has a glossy finish. B: The surface of the cured material lacks gloss.

[0132] [3. Evaluation of heat resistance] The developed laminate, which was subjected to the evaluation of "(1) Exposure conditions with carrier film" in "2. Evaluation of surface hardening properties" above, was exposed to UV conveyor type exposure at 2 J / cm². 2 The material irradiated with light (wavelength 365 nm) was heat-treated in a hot air circulating dryer at 170°C for 1 hour to obtain a heat-treated laminate. The laminate was left for 100 hours under saturated water vapor conditions of 120°C and 2 atmospheres, and the surface of the laminate, i.e., the appearance of the cured photosensitive resin film, was observed and evaluated according to the evaluation criteria below. A: There is no peeling or swelling. B: There is peeling or blistering.

[0133] [Preparation of photosensitive resin composition] Examples 1-10, Comparative Examples 1-5 (1) Production of photosensitive resin composition Each component was blended according to the formulation shown in Table 1 (the units of the values ​​in the table are parts by mass, and in the case of solutions, the amount is on a solid content basis), and kneaded using a three-roll mill and a self-rotating mixer. Then, methyl ethyl ketone was added to obtain a photosensitive resin composition to a solid content concentration of 65% by mass. (2) Manufacturing of photosensitive resin film A polyethylene terephthalate film (manufactured by Teijin Limited, trade name "G2-16", thickness 16 μm) was used as a carrier film, and the photosensitive resin composition prepared in each example was coated onto the carrier film to a thickness of 25 μm after drying. Then, it was dried at 75°C for 30 minutes using a hot air convection dryer to form a photosensitive resin film with a carrier film. Next, a polyethylene film (manufactured by Tamapoly Co., Ltd., product name "NF-15") was laminated as a protective film to the side of the photosensitive resin film opposite to the side in contact with the carrier film, thereby obtaining a photosensitive resin film with a carrier film and a protective film.

[0134] The above evaluations were performed using the fabricated photosensitive resin film. The results are shown in Table 1.

[0135] [Table 1]

[0136] The details of components (A), (C), (H), and (J) used in Table 1 are as follows.

[0137] [(A) component] • Compounds containing carboxyl and acryloyl groups: Manufactured by Nippon Kayaku Co., Ltd., trade name "ZXR-1889H", acid value: 110 mg KOH / g, weight-average molecular weight: 3,000-4,000

[0138] [(C) component] • Polyfunctional maleimide compound: Biphenyl aralkyl type maleimide resin, manufactured by Nippon Kayaku Co., Ltd., trade name "MIR-3000", maleimide group equivalent: 393 g / eq • Polyfunctional allyl compound: diallyl isocyanurate compound, manufactured by Shikoku Chemicals Co., Ltd., product name "LDAIC" • Polyfunctional nadiimide compounds: Compounds represented by the following general formula (1)

[0139] [ka]

[0140] • Polybutadiene-based elastomer containing 1,2-vinyl groups: butadiene-styrene copolymer, manufactured by Cray Valley, trade name "Ricon100", number average molecular weight: 4,500 • Acid anhydride-modified polybutadiene: Manufactured by Cray Valley, trade name "Ricon131MA17", number average molecular weight: 5,400, number of acid anhydride groups per molecule: 9

[0141] [(H) component: epoxy resin] • Naphthol-type epoxy resin: Manufactured by Nippon Steel & Sumitomo Metal Corporation, product name "ESN-475V", epoxy group equivalent: 325g / eq • Biphenyl aralkyl epoxy resin: Manufactured by Nippon Kayaku Co., Ltd., product name "NC-3000-L", epoxy group equivalent: 272 g / eq

[0142] [(J) Ingredients: Other ingredients] • Surface modifier: Silicone-based foam stabilizer, manufactured by Dow-Toray Corporation, product name "SH-193"

[0143] Table 1 shows that the cured products formed from the photosensitive resin compositions of Examples 1 to 10 of this embodiment, which contain components (A) to (E), all had low dielectric loss tangent (Df) and excellent heat resistance. On the other hand, Comparative Example 1, which did not use component (E), had a lower dielectric loss tangent (Df) than Example 1, which had the same composition except for component (E). Furthermore, Comparative Example 2, which did not use component (E), had inferior dielectric loss tangent (Df) and heat resistance compared to Example 2, which had the same composition except for component (E). Furthermore, Comparative Example 3, which did not use components (E), (H), and (I), failed to form an evaluable cured product due to poor curing. Furthermore, Comparative Example 4, which did not use components (C), (E), (H), and (I), was inferior in relative permittivity (Dk), dielectric loss tangent (Df), and heat resistance. Furthermore, Comparative Example 5, which did not use components (C) and (E), had good heat resistance, but was inferior in relative permittivity (Dk) and dielectric loss tangent (Df). These results show that the photosensitive resin composition of this embodiment can improve the dielectric loss tangent (Df) without reducing heat resistance. [Explanation of Symbols]

[0144] 100A Multilayer Printed Circuit Board 101 circuit board 102 Circuit Patterns 103 Photosensitive layer 104 Interlayer insulating layer 105 Beer 106 Seed Layer 107 Resist Patterns 108 Copper circuit layer 109 Solder Resist Layer

Claims

1. (A) Compounds having an acidic substituent and a (meth)acryloyl group, (B) A (meth)acrylate compound having two or more (meth)acryloyl groups, (C) A compound having two or more ethylenically unsaturated groups other than (meth)acryloyl groups, (D) Photopolymerization initiator, (E) Organic peroxides and (F) Inorganic filler and It contains, The aforementioned component (A) includes an alicyclic skeleton represented by the following general formula (A-1), A photosensitive resin composition in which component (C) is a compound having two or more vinyl groups, and the compound having two or more vinyl groups is a polybutadiene elastomer having 1,2-vinyl groups. 【Chemistry 1】 (In the formula, R Ａ１ m represents an alkyl group having 1 to 12 carbon atoms and may be substituted anywhere in the above alicyclic skeleton. １ (The integer is between 0 and 6. * indicates a connection point.)

2. The photosensitive resin composition according to claim 1, wherein the acid value of component (A) is 20 to 200 mg KOH / g, and the weight-average molecular weight of component (A) is 500 to 30,000.

3. The photosensitive resin composition according to claim 1 or 2, wherein the content of component (A) is 10 to 80% by mass on a total basis of component (A), component (B), component (C), component (D), component (E) and any resin component in the photosensitive resin composition.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of component (B) is 10 to 80 parts by mass per 100 parts by mass of component (A).

5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the content of component (C) is 1 to 80% by mass on a basis of the total amount of component (A), component (B), component (C), component (D), component (E) and any resin component in the photosensitive resin composition.

6. The photosensitive resin composition according to any one of claims 1 to 5, wherein the content of component (D) is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (A) and component (B).

7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the content of component (F) is 10 to 70% by mass based on the total solid content of the photosensitive resin composition.

8. The photosensitive resin composition according to any one of claims 1 to 7, wherein the (F) component is silica.

9. Furthermore, the photosensitive resin composition according to any one of claims 1 to 8, further comprising (G) a thiol compound.

10. A photosensitive resin composition according to any one of claims 1 to 9, for use in forming photovias.

11. The photosensitive resin composition according to any one of claims 1 to 10, wherein the dielectric loss tangent (Df) of the cured product at 10 GHz is 0.0040 to 0.0100.

12. A photosensitive resin film formed using the photosensitive resin composition according to any one of claims 1 to 11.

13. A photosensitive resin film according to claim 12, wherein the thickness is 1 to 100 μm.

14. A multilayer printed circuit board comprising an interlayer insulating layer formed using the photosensitive resin composition according to any one of claims 1 to 11 or the photosensitive resin film according to claim 12 or claim 13.

15. A semiconductor package comprising a multilayer printed circuit board as described in claim 14.

16. A method for manufacturing a multilayer printed circuit board, including (1) to (4) below. (1) Laminating the photosensitive resin film according to claim 12 or 13 to one or both sides of a circuit board. (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 interlayer insulating layer.

Images