Thermosetting resin composition and its uses

Abstract

To provide a thermosetting resin composition that can give a cured product having excellent thermostability, and low dielectric constants and dielectric loss tangents, and excellent dielectric properties.SOLUTION: A thermosetting resin composition contains (A) a thermosetting resin and (B) a crosslinker, the thermosetting resin (A) containing a structural unit a having a norbornene skeleton, and a structural unit b represented by the general formula (2), with a weight average molecular weight of 500 or more and 10,000 or less. In the formula (2), Q is a group having a terminal double bond.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition and its use. [Background technology]

[0002] BACKGROUND ART Norbornene-based resins have been used for a variety of applications as molded articles because of their excellent electrical properties, optical properties, and low moisture absorption.

[0003] Patent Document 1 discloses a resin composition containing a cyclic olefin homopolymer having a glass transition temperature of 101 to 160°C, a fibrous conductive filler, and another elastomer. It is stated that a molding material obtained from the resin composition has excellent mechanical strength, heat resistance, and conductivity.

[0004] Patent Document 2 discloses a method for producing a polycyclic olefin polymer by polymerizing a polycyclic olefin monomer in the presence of a palladium catalyst complex and a chain transfer / activation agent.

[0005] Patent Document 3 discloses a cyclic olefin binary copolymer containing specific molar amounts of repeating units derived from a norbornene monomer having an epoxy group and repeating units derived from a norbornene monomer having a vinyl group. The document also describes that the weight-average molecular weight of this cyclic olefin binary copolymer is 1,000 g / mol to 100,000 g / mol. Furthermore, it also describes that a cured product obtained from a cyclic olefin binary copolymer containing this repeating unit has excellent adhesive strength with copper foil and improved dielectric loss at 10 GHz. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-231171 [Patent Document 2] Special Publication No. 2010-523766 [Patent Document 3] Special Publication No. 2019-506488 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the polymers described in Patent Documents 1 and 2 are not thermosetting, have low solubility in organic solvents, and furthermore, there is room for improvement in the low dielectric properties of the resulting cured products. The cured product of the cyclic olefin-based binary copolymer described in Patent Document 3 has room for improvement in terms of low dielectric properties. [Means for solving the problem]

[0008] The present inventors have discovered that a thermosetting resin composition containing a specific structural unit constituting a cyclic olefin copolymer, which is a thermosetting resin, and further containing a crosslinking agent can give a cured product having low dielectric constant and dielectric loss tangent and excellent dielectric properties, and have completed the present invention. That is, the present invention can be shown as follows.

[0009] According to the present invention, (A) a thermosetting resin; (B) a crosslinking agent; Including, The thermosetting resin (A) is A structural unit a represented by the following general formula (1), A structural unit b represented by the following general formula (2), and a weight average molecular weight of 500 or more and 10,000 or less. [ka] (In general formula (1), R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (excluding groups having a terminal double bond); and n is 0, 1, or 2. [ka] (In the general formula (2), Q represents a group having a terminal double bond, and R 1 , R 2 , and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m is 0, 1, or 2.

[0010] According to the present invention, A carrier substrate; A resin film with a carrier is provided, the resin film being made of the thermosetting resin composition and provided on the carrier substrate.

[0011] According to the present invention, A prepreg is provided which contains a fiber substrate in a resin layer made of the thermosetting resin composition.

[0012] According to the present invention, A laminate is provided in which a metal layer is disposed on at least one surface of the prepreg.

[0013] According to the present invention, There is provided a printed wiring board having an insulating layer made of a cured product of the thermosetting resin composition.

[0014] According to the present invention, the printed wiring board; and a semiconductor element mounted on a circuit layer of the printed wiring board or embedded in the printed wiring board. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a thermosetting resin composition that can give a cured product having excellent heat resistance, low dielectric constant and dielectric loss tangent, and excellent dielectric properties. In other words, it is possible to provide a thermosetting resin composition that has an excellent balance of these properties. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 2 is a cross-sectional view showing an example of the configuration of a resin film with a carrier in the present embodiment. [Figure 2] 1 is a cross-sectional view showing an example of the configuration of a printed wiring board according to an embodiment of the present invention. [Figure 3] 1 is a cross-sectional view showing an example of the configuration of a semiconductor device according to an embodiment of the present invention. [Figure 4] 5A to 5C are cross-sectional views showing steps in an example of a manufacturing process for a printed wiring board according to the present embodiment. [Figure 5] 1 is a cross-sectional view showing an example of the configuration of a printed wiring board according to an embodiment of the present invention. [Figure 6] 1 is a cross-sectional view showing an example of the configuration of a printed wiring board according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by similar reference numerals, and their description will be omitted where appropriate. Furthermore, "A to B" represents "A or more" to "B or less" unless otherwise specified.

[0018] The thermosetting resin composition of the present embodiment contains a thermosetting resin (A) and a crosslinking agent (B).

[0019] [Thermosetting resin (A)] The thermosetting resin (A) of this embodiment contains a structural unit a represented by the following general formula (1) and a structural unit b represented by the following general formula (2), and has a weight average molecular weight of 500 or more and 10,000 or less.

[0020] [ka]

[0021] In the general formula (1), n is 0, 1 or 2, and preferably 0 or 1. R 1 , R 2, R 3 and R 4 are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms. In this embodiment, the hydrocarbon group having 1 to 30 carbon atoms does not include a group having a terminal double bond. 1 Comrade, R 2 Comrade, R 3 R 4 They may be the same or different.

[0022] Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, and a cycloalkyl group.

[0023] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0024] Examples of the alkenyl group include an allyl group, a pentenyl group, etc. Examples of the alkynyl group include an ethynyl group. The alkylidene group includes, for example, an ethylidene group.

[0025] Aryl groups include, for example, phenyl, naphthyl, and anthracenyl groups, and aralkyl groups include, for example, benzyl and phenethyl groups.

[0026] Examples of the alkaryl group include tolyl and xylyl groups, and examples of the cycloalkyl group include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

[0027] The hydrocarbon group having 1 to 30 carbon atoms may contain at least one atom selected from O, N, S, P and Si in its structure.

[0028] In this embodiment, the hydrocarbon group having 1 to 30 carbon atoms is preferably a hydrocarbon group having 1 to 15 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 carbon atoms. Furthermore, the hydrocarbon group having 1 to 30 carbon atoms is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and even more preferably an alkyl group having 1 to 10 carbon atoms.

[0029] Examples of the substituent of the substituted hydrocarbon group having 1 to 30 carbon atoms include a hydroxyl group, an amino group, a cyano group, an ester group, an ether group, an amide group, and a sulfonamide group, and the group may be substituted with at least one of these groups.

[0030] In this embodiment, R 1 , R 2 , R 3 and R 4 Preferably, one of the above is a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and the rest are hydrogen atoms, and more preferably, all are hydrogen atoms. In this embodiment, the thermosetting resin (A) can contain at least one of the above structures as the structural unit a.

[0031] [ka]

[0032] In the general formula (2), m is 0, 1 or 2, and preferably 0 or 1. Q represents a group having a terminal double bond. The group having a terminal double bond can include a vinyl group, an allyl group, a (meth)acryloyl group, a vinylphenyl group, or a maleimide group.

[0033] Examples of the group having a terminal double bond include a vinyl group, an allyl group, a (meth)acryloyl group, a vinylphenyl group, a (meth)acryloylalkyl group, a (meth)acryloyloxyalkyl group, a vinylphenylalkyl group, and a vinylphenyloxyalkyl group, and these groups may contain an ether bond or a thioether bond in the alkylene chain.

[0034] R 1 , R 2 , and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In this embodiment, R 1 , R 2 , and R 3 It is preferable that one of them is an alkyl group having 1 to 3 carbon atoms and the rest are hydrogen atoms, and it is more preferable that all of them are hydrogen atoms.

[0035] In this embodiment, the thermosetting resin (A) can contain at least one of the above structures as the structural unit b. Specific examples of the structural unit b represented by general formula (2) include a structural unit derived from 5-vinyl-2-norbornene, a structural unit derived from butenylnorbornene, a structural unit derived from hexenylnorbornene, and a structural unit represented by the following formula, and one or more selected from these can be used.

[0036] [ka]

[0037] In the thermosetting resin (A) of this embodiment, from the viewpoint of the effects of the present invention, and further from the viewpoint of thermosetting property and solvent solubility, the molar ratio of the structural unit b to the structural unit a (b / a) can be 0.1 or more and 4 or less, preferably 0.1 or more and 3.5 or less, and more preferably 0.1 or more and 3 or less.

[0038] The thermosetting resin (A) of this embodiment contains the structural unit a and the structural unit b, and may contain structural units derived from other monomers in addition to these structural units.

[0039] Other monomers include indene, styrene, acenaphthylene, norbornadiene, terpene compounds (for example, pinene, limonene, etc.), linear alkenes (for example, pentene, etc.), cyclic alkenes (cyclohexene, etc.), and the like.

[0040] The thermosetting resin (A) of this embodiment does not contain structural units derived from ethylene or α-olefin, nor does it contain structural units derived from maleic acid, maleimide, maleic anhydride, etc., which affect the dielectric constant.

[0041] From the viewpoint of low dielectric constant, the thermosetting resin (A) has a total amount of structural units a and b of 80 mol % or more, preferably 90 mol %, more preferably 95 mol % or more, based on 100 mol % of all structural units. The upper limit is not particularly limited, but is 100 mol % or less.

[0042] The weight average molecular weight (Mw) of the thermosetting resin (A) is 500 or more and 10,000 or less, preferably 600 or more and 8,000 or less, and more preferably 700 or more and 7,000 or less, from the viewpoint of the effects of the present invention, and further from the viewpoint of thermosetting property and solvent solubility.

[0043] The thermosetting resin (A) of this embodiment may have a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of, for example, 1.0 to 6.0, preferably 1.2 to 5.0, and more preferably 1.5 to 4.0. Mw / Mn is a polydispersity that indicates the width of the molecular weight distribution.

[0044] The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are polystyrene-equivalent values obtained from a calibration curve of standard polystyrene (PS) obtained by, for example, GPC (Gel Permeation Chromatography) measurement. The measurement conditions are, for example, as follows: Tosoh gel permeation chromatography device HLC-8320GPC Column: Tosoh TSK-GEL Supermultipore HZ-M Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 0.5 wt%

[0045] The thermosetting resin (A) of this embodiment has a solubility in toluene of 30 wt % or more, preferably 50 wt % or more, and more preferably 60 wt % or more at 25° C. The solubility is calculated by the following formula. Formula: [Weight of thermosetting resin (A) / (Weight of thermosetting resin (A) + Weight of toluene)] x 100 Because of this high solubility in organic solvents, it has excellent film-forming properties and compatibility with other resins.

[0046] The thermosetting resin (A) of this embodiment has excellent melting properties (or excellent embeddability during substrate production), and its melting temperature is, for example, 250°C or lower, preferably 230°C or lower, and more preferably 200°C or lower. The lower limit of the melting temperature is 50°C or higher, preferably 60°C or higher, and more preferably 70°C or higher. Because the thermosetting resin (A) of this embodiment is thermosetting and has the above-mentioned melting temperature, it has excellent production stability for interlayer insulating films that constitute the multilayer wiring structure of semiconductor elements, build-up layers or core layers that constitute circuit boards, and the like, and can be suitably used for these semiconductor applications.

[0047] [Method for synthesizing thermosetting resin (A)] The method for synthesizing the thermosetting resin (A) of this embodiment can be, for example, The method includes a step of reacting a compound a1 represented by the following general formula (1a) with a compound b1 represented by the following general formula (2a) in an organic solvent in the presence of a polymerization catalyst and a chain transfer agent.

[0048] [ka]

[0049] In general formula (1a), R 1 , R 2 , R 3 and R 4 , n has the same meaning as in general formula (1).

[0050] [ka]

[0051] In general formula (2a), Q, R 1 , R 2 , R 3 , m has the same meaning as in general formula (1). Specific examples of the compound b1 represented by general formula (2a) include 5-vinyl-2-norbornene, butenylnorbornene, hexenylnorbornene, and compounds represented by the following formulae (from left to right: bicyclo[2.2.1]hept-5-en-2-yl methacrylate, 2-propenoic acid 2-methyl-bicyclo[2.2.1]hept-5-en-2-ylmethyl ester, 2-propenoic acid bicyclo[2.2.1]hept-5-en-2-ylmethyl ester, 5-[[(4-ethenylphenyl)methoxy]methyl]bicyclo[2.2.1]hept-2-ene), and one or more selected from these can be used.

[0052] [ka]

[0053] In this embodiment, first, the compound a1, the compound b1, and a chain transfer agent are dissolved in an organic solvent, and then the solution is preheated to about 40°C to 85°C. The molar ratio (b1 / a1) of the compound b1 represented by the following general formula (2a) to the compound a1 represented by the general formula (1a) can be set to 0.1 or more and 4 or less, preferably 0.1 or more and 3.5 or less, and more preferably 0.1 or more and 3 or less, from the viewpoint of thermosetting properties.

[0054] A catalyst dilution solution is prepared by diluting the polymerization catalyst and, if necessary, a cocatalyst in an organic solvent, and the diluted catalyst solution is added to the heated mixed solution. The catalyst dilution solution may be added all at once or dropwise. Examples of dilution solvents include toluene, ethyl acetate, and tetrahydrofuran, and one or more of these can be used in combination.

[0055] The diluted catalyst solution is added to the mixed solution, and then heated for a predetermined period of time to carry out solution polymerization. In this case, the heating temperature may be, for example, about 30° C. to 200° C., and the heating time may be, for example, 0.5 to 72 hours. It is more preferable to carry out solution polymerization after removing dissolved oxygen in the solvent by nitrogen bubbling. If necessary, a molecular weight modifier can be used.

[0056] The organic solvent may be one or more selected from ketone solvents, ether solvents, ester solvents, acyclic aliphatic alcohol solvents, aromatic solvents, etc. Specific examples of these organic solvents include cyclopentanone, heptanone, anisole, butanol, toluene, etc. One or more selected from these may be used.

[0057] By using these organic solvents, it is possible to obtain a cyclic olefin resin that is thermosetting, has excellent solubility in organic solvents, and also has excellent low dielectric properties.

[0058] Examples of the chain transfer agent include trialkylsilane compounds such as trimethylsilane, triethylsilane, and tributylsilane, and cyclobutene compounds such as bicyclo[4.2.0]octa-7-ene, etc. These chain transfer agents may be used alone or in combination of two or more.

[0059] By using these chain transfer agents, it is possible to obtain a cyclic olefin resin that is thermosetting, has excellent solubility in organic solvents, and also has excellent low dielectric properties. In this embodiment, from the viewpoint of obtaining a desired cyclic olefin resin, it is more preferable to use the organic solvent and the chain transfer agent in combination.

[0060] The polymerization catalyst is not particularly limited as long as it allows addition polymerization to proceed, but for example, a palladium complex or nickel complex may be coordinated with a phosphine, diimine, or nitrile ligand to form a counter anion, etc. One or more of these may be used.

[0061] Examples of the palladium complex include Palladium(II) (acetonitrile)bis(triisopropylphosphine)acetate tetrakis(2,3,4,5,6-pentafluorophenyl)borate, allylpalladium complexes such as π-allylpalladium chloride dimer; Palladium organic carboxylates such as palladium acetate, propionate, maleate, and naphthoate; Palladium organic carboxylic acid complexes such as palladium acetate triphenylphosphine complex, palladium acetate tri(m-tolyl)phosphine complex, palladium acetate tricyclohexylphosphine complex, and palladium acetate triisopropylphosphine complex; Palladium organic sulfonates such as palladium dibutyl phosphite and p-toluenesulfonate; β-diketone compounds of palladium such as bis(acetylacetonato)palladium, bis(hexafluoroacetylacetonato)palladium, bis(ethylacetoacetate)palladium, and bis(phenylacetoacetate)palladium;

[0062] Examples thereof include dichlorobis(triphenylphosphine)palladium, bis[tri(m-tolylphosphine)]palladium, dibromobis[tri(m-tolylphosphine)]palladium, and halide complexes of palladium such as acetonyltriphenylphosphonium complex.

[0063] Examples of the phosphine ligand include triphenylphosphine, dicyclohexylphenylphosphine, cyclohexyldiphenylphosphine, and tricyclohexylphosphine.

[0064] Examples of the counter anion include tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbenium tetrakis(2,4,6-trifluorophenyl)borate, triphenylcarbenium tetraphenylborate, and tributylammonium tetrakis(pentafluorophenyl)borate. The polymerization catalyst can be used in an amount of 1 ppm to 1000 ppm of norbornene-based monomers (compound a1 and compound b1).

[0065] The pre-promoter preferably contains an ion complex containing a weakly coordinating anion salt. That is, when synthesizing the addition-type norbornene-based resin, it is preferable to add a promoter in addition to the catalyst. This can further increase the polymerization rate of the addition-type norbornene-based monomer.

[0066] The co-catalyst is not particularly limited, but examples thereof include alkylaluminum, Lewis acids, and ionic complexes containing weakly coordinating anion (WCA) salts, and among these, ionic complexes containing weakly coordinating anion (WCA) salts are preferred.

[0067] Furthermore, the promoter is more preferably one represented by the following formula (i): [C]e [WCA] d Formula (i) (In the above formula, C represents a proton (H + ), an organic radical-containing cation, or an alkali metal, alkaline earth metal, or transition metal cation, WCA is as defined above, and e and d are numbers determined to balance the electronic charge on the overall salt complex of the cation complex (C) and the weakly coordinating anion salt (WCA), respectively.

[0068] The ionic complex containing the weakly coordinating anion (WCA) salt is not particularly limited, but may be lithium(diethyl ether) 2.5 Tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(pentafluorophenyl)borate, dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, H(OEt2) x Examples include tetrakis(pentafluorophenyl)borate, tetrakis[(4-methyl)-α,α-bis(trifluoromethyl)benzenemethanolato-κO]aluminate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, trialkyl and triarylphosphonium tetrakis(pentafluorophenyl)borate, and trityl tetrakis(pentafluorophenyl)borate. The co-catalyst can be used in an amount of 1 ppm to 1000 ppm of the norbornene-based monomers (compound a1 and compound b1).

[0069] The resulting reaction liquid containing the thermosetting resin (A) is added to an alcohol such as hexane or methanol to precipitate the thermosetting resin (A). The thermosetting resin (A) is then filtered, washed with an alcohol such as hexane or methanol, and then dried. In this embodiment, for example, the thermosetting resin (A) can be synthesized in this manner.

[0070] [Resin varnish] In this embodiment, a polymer solution (resin varnish) in which the thermosetting resin (A) is dissolved in an organic solvent can be provided. In this polymer solution (resin varnish), at a liquid temperature of 25° C., it is sufficient that at least a portion of the polymer is dissolved, but it is preferable that all of the polymer is dissolved.

[0071] Examples of organic solvents used in resin varnishes include acetone, ethyl acetate, cyclohexane, heptane, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve-based solvents, carbitol-based solvents, anisole, N-methylpyrrolidone, propylene glycol monomethyl ether, methyl ether acetate, toluene, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, etc. The organic solvent may be used alone or in combination of two or more selected from these.

[0072] The lower limit of the thermosetting resin content in the resin varnish is, for example, 5% by mass or more, preferably 7% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to 100% by mass of the resin varnish. On the other hand, the upper limit of the thermosetting resin content in the resin varnish is, for example, 80% by mass or less, preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less, relative to 100% by mass of the resin varnish. By keeping the content within such a numerical range, the handleability of the resin varnish can be improved, and a resin material with excellent heat resistance can be achieved.

[0073] [Thermosetting resin composition] The thermosetting resin composition of this embodiment can be prepared using a resin varnish and contains the above-mentioned thermosetting resin (A) and a crosslinking agent (B). The curable resin composition of this embodiment can provide a low dielectric constant material.

[0074] [Crosslinking agent (B)] The crosslinking agent (B) can crosslink the thermosetting resin (A), and any known crosslinking agent can be used as long as the effects of the present invention are achieved. However, it is preferable that the crosslinking agent (B) contains a crosslinking agent (b1) that is liquid at room temperature (25°C). The thermosetting resin composition of this embodiment contains the crosslinking agent (b1), and thus can give a cured product with excellent heat resistance and low dielectric properties.

[0075] The crosslinking agent (b1), which is liquid at room temperature (25°C), may contain a crosslinking agent having two or more reactive groups, such as a vinyl group, an allyl group, a (meth)acryloyl group, a vinylphenyl group, and a maleimide group.

[0076] Examples of crosslinking agents having two or more reactive groups include styrene-butadiene rubber, polybutadiene rubber, triallyl isocyanurate, and divinylbenzene, and at least one selected from these can be used. The crosslinking agent (b1) can be contained in an amount of 5 to 200 parts by mass, preferably 10 to 180 parts by mass, and more preferably 20 to 150 parts by mass, per 100 parts by mass of the thermosetting resin (A).

[0077] The crosslinking agent (B) preferably contains, in addition to the crosslinking agent (b1), a crosslinking agent (b2) that is solid at room temperature (25° C.) By further including the crosslinking agent (b2), a cured product with excellent heat resistance and low dielectric properties can be obtained.

[0078] The crosslinking agent (b2) that is solid at room temperature (25°C) can contain a crosslinking agent having a weight-average molecular weight of 1,000 or more and 20,000 or less, preferably 1,000 or more and 10,000 or less, and more preferably 1,000 or more and 7,000 or less. If the weight-average molecular weight of the crosslinking agent is within this range, the crosslinking agent has excellent solvent solubility and compatibility, and the viscosity of the varnish is reduced, resulting in excellent processability.

[0079] Examples of the crosslinking agent (b2) include terminal methacrylate-modified polyphenylene ether, styrene-modified polyphenylene ether, bisphenol A dimethacrylate, and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, and at least one selected from these can be used.

[0080] When the crosslinking agent (B) contains the crosslinking agent (b2), the crosslinking agent (b2) can be contained in an amount of 10 parts by mass or more and 200 parts by mass or less, preferably 20 parts by mass or more and 180 parts by mass or less, and more preferably 30 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the thermosetting resin (A). Furthermore, the weight ratio (b1:b2) of the crosslinking agent (b1) to the crosslinking agent (b2) can be set to 5:95 to 95:5, preferably 20:80 to 80:20, and more preferably 25:75 to 75:25.

[0081] [Radical polymerization initiator (C)] The thermosetting resin composition of the present embodiment preferably further contains a radical polymerization initiator (C).

[0082] Examples of the radical polymerization initiator (C) include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-t-butylperoxy)cyclohexane, and t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butylperoxy)-2-methylcyclohexane, t-butyl hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexane, α,α'-bis(t-butylperoxy)diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexyne, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl Peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate, α,α'-bis(neodecanoylperoxy)diisopropylbenzene, cumyl peroxyneodecanoate, 1,1,3,3,-Tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxy Examples of suitable peroxy groups include tert-butylperoxy laurate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, t-butylperoxyacetate, t-hexylperoxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis(t-butylperoxy)isophthalate, t-butylperoxyallyl monocarbonate, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone. These may be used alone or in combination to control curing properties.

[0083] The radical polymerization initiator (C) can be used in an amount of 0.1 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total of the thermosetting resin (A) and the crosslinking agent (B).

[0084] Filler The thermosetting resin composition of the present embodiment preferably further contains a filler (D). Examples of the filler (D) include silver, titanium oxide, silica, and mica. Among these, silica is preferred. This allows the cured product of the thermosetting resin composition to have excellent thermal properties. The shape of the silica filler may be crushed silica or spherical silica, with spherical silica being preferred.

[0085] The content of the filler (D) is not particularly limited, but is preferably 15 to 70 mass %, more preferably 20 to 70 mass %, based on the total mass of the thermosetting resin composition, which provides a cured product of the thermosetting resin composition with excellent thermal properties.

[0086] (Other ingredients) The thermosetting resin composition of the present embodiment may contain other components such as a resin other than a thermosetting resin, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a surfactant, a silane-based, aluminum-based, or titanium-based coupling agent, a polyhydric phenol compound, or an organic solvent, depending on the purpose and required characteristics of each application.

[0087] <Thermosetting resin composition and cured product thereof> The thermosetting resin composition of the present embodiment can be prepared by mixing the above-mentioned components using the resin varnish described above. The thermosetting resin composition of the present embodiment can provide a low dielectric constant material.

[0088] The thermosetting resin composition of the present embodiment contains a polymer obtained by polymerizing a predetermined norbornene-based monomer. It is thermosetting, has excellent handleability, and can provide a low-dielectric-constant material. Therefore, it has excellent manufacturing stability for interlayer insulating films that constitute the multilayer wiring structure of semiconductor elements, build-up layers or core layers that constitute circuit boards, and the like, and can be suitably used for these semiconductor applications.

[0089] The curable resin composition of this embodiment can be thermally cured to obtain a cured product, after removing the organic solvent by drying or the like as necessary. Thermal curing can be carried out in air, a nitrogen atmosphere, a vacuum, or the like. When transparency is required for the resulting cured product, it is preferable to carry out the thermal curing in a nitrogen atmosphere or a vacuum, or to use an antioxidant in combination.

[0090] The glass transition temperature of the cured product (molded product) of this embodiment is preferably 120°C or higher, more preferably 140°C or higher. A glass transition temperature of 120°C or higher can satisfy the heat resistance required during molding. The upper limit of the glass transition temperature is not particularly limited, but is 300°C or lower.

[0091] The dielectric constant of the cured product (molded product) of this embodiment at a frequency of 10 GHz can be 2.8 or less, preferably 2.6 or less, and more preferably 2.5 or less when the cured product does not contain filler or glass cloth, and can be 4.0 or less, preferably 3.8 or less, and more preferably 3.5 or less when the cured product contains filler or glass cloth. This allows the cured product to be used as a low-dielectric-constant material.

[0092] The cured product (molded article) of this embodiment has a dielectric loss tangent (tan δ) of 0.007 or less, preferably 0.006 or less, and more preferably 0.005 or less, when measured at a frequency of 10 GHz, thereby further improving the dielectric properties of the cured product.

[0093] [Application] The thermosetting resin composition of the present embodiment may be used in any form, including, but not limited to, a resin film made of the thermosetting resin composition, a resin film with a carrier in which the resin film is provided on a carrier substrate, a prepreg obtained by impregnating a fiber substrate with the thermosetting resin composition, a metal-clad laminate in which a metal layer is disposed on at least one surface of the cured product of the prepreg, a resin substrate provided with an insulating layer made of a cured product of the thermosetting resin composition, and a printed wiring board in which a circuit layer is formed on the surface of the metal-clad laminate or the resin substrate.

[0094] (resin film with carrier) Next, the resin film with a carrier of this embodiment will be described. FIG. 1 is a cross-sectional view showing an example of the configuration of a resin film 100 with a carrier in this embodiment.

[0095] 1, the carrier-attached resin film 100 of this embodiment can include a carrier substrate 12 and a resin film 10 made of the thermosetting resin composition provided on the carrier substrate 12. This can improve the handleability of the resin film 10. The resin film 100 with a carrier may be in a roll shape that can be wound up, or in a sheet shape such as a rectangular shape.

[0096] In this embodiment, for example, a polymer film or a metal foil can be used as the carrier substrate 12. The polymer film is not particularly limited, but examples thereof include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, release paper such as silicone sheets, and heat-resistant thermoplastic resin sheets such as fluorine-based resins and polyimide resins. The metal foil is not particularly limited, but examples thereof include copper and / or copper-based alloys.

[0097] Examples include gold, aluminum and / or aluminum-based alloys, iron and / or iron-based alloys, silver and / or silver-based alloys, gold and / or gold-based alloys, zinc and / or zinc-based alloys, nickel and / or nickel-based alloys, and tin and / or tin-based alloys. Among these, a sheet made of polyethylene terephthalate is the most preferable because it is inexpensive and the peel strength can be easily adjusted. This makes it easy to peel from the carrier-attached resin film 100 with an appropriate strength.

[0098] The lower limit of the thickness of the resin film 10 is not particularly limited, but may be, for example, 1 μm or more, 3 μm or more, or 5 μm or more. This allows the mechanical strength of the resin film 10 to be increased. On the other hand, the upper limit of the thickness of the resin film 10 is not particularly limited, but may be, for example, 500 μm or less, 300 μm or less, or 100 μm or less. This allows the semiconductor device to be made thinner.

[0099] The thickness of the carrier substrate 12 is not particularly limited, but may be, for example, 10 to 100 μm or 10 to 70 μm, which is preferable because it allows for good handling when producing the carrier-attached resin film 100.

[0100] The resin film 100 with a carrier of this embodiment may be a single layer or a multilayer, and may contain one or more types of resin films 10. When the resin sheet is multilayer, it may be composed of the same type or different types. In addition, the resin film 100 with a carrier may have a protective film on the outermost layer side of the resin film 10.

[0101] In this embodiment, the method for forming the carrier-attached resin film 100 is not particularly limited, but for example, a method can be used in which a varnish-like thermosetting resin composition is applied to the carrier substrate 12 using various coater devices to form a coating film, and then the coating film is appropriately dried to remove the solvent.

[0102] (Resin substrate) The resin substrate of the present embodiment can have an insulating layer made of a cured product of a thermosetting resin composition. Such a resin substrate can be configured to contain no glass fibers and can be used as a printed wiring board.

[0103] (prepreg) The prepreg of this embodiment is obtained by impregnating a fiber substrate with the thermosetting resin composition. For example, the prepreg can be used as a sheet-like material obtained by impregnating a fiber substrate with the thermosetting resin composition and then semi-curing the material. A sheet-like material having such a structure has excellent properties such as dielectric properties and mechanical and electrical connection reliability under high temperature and humidity conditions, and is suitable for producing insulating layers for printed wiring boards.

[0104] The method for impregnating a fiber substrate with a thermosetting resin composition is not particularly limited, but examples include a method in which the thermosetting resin composition is dissolved in a solvent to prepare a resin varnish and the fiber substrate is immersed in the resin varnish, a method in which the resin varnish is applied to the fiber substrate using various coaters, a method in which the resin varnish is sprayed onto the fiber substrate using a sprayer, and a method in which both sides of the fiber substrate are laminated with the resin film consisting of the thermosetting resin composition.

[0105] In this embodiment, the prepreg can be used to form, for example, an insulating layer in a build-up layer or an insulating layer in a core layer of a printed wiring board. When the prepreg is used to form an insulating layer in a core layer of a printed wiring board, for example, two or more prepregs can be stacked and the resulting laminate can be heat-cured to form an insulating layer for the core layer.

[0106] Examples of the fiber substrate include, but are not limited to, glass fiber substrates such as glass woven fabric and glass nonwoven fabric; polyamide resin fibers such as polyamide resin fibers, aromatic polyamide resin fibers, and wholly aromatic polyamide resin fibers; polyester resin fibers such as polyester resin fibers, aromatic polyester resin fibers, and wholly aromatic polyester resin fibers; synthetic fiber substrates composed of woven or nonwoven fabrics primarily composed of polyimide resin fibers or fluororesin fibers; and paper substrates primarily composed of kraft paper, cotton linter paper, or a mixed paper of linter and kraft pulp. Any of these can be used. Among these, glass fiber substrates are preferred. This allows for the production of a resin substrate with low water absorption, high strength, and low thermal expansion.

[0107] The thickness of the fiber base material is not particularly limited, but is preferably 5 μm to 150 μm, more preferably 10 μm to 100 μm, and even more preferably 12 μm to 90 μm. Use of a fiber base material having such a thickness can further improve the handleability during prepreg production.

[0108] When the thickness of the fiber substrate is equal to or less than the upper limit, the impregnation of the thermosetting resin composition into the fiber substrate is improved, and the occurrence of strand voids and a decrease in insulation reliability can be suppressed. Furthermore, the formation of through-holes using carbon dioxide, UV, excimer, or other lasers can be facilitated. Furthermore, when the thickness of the fiber substrate is equal to or greater than the lower limit, the strength of the fiber substrate and prepreg can be improved. As a result, handling can be improved, prepreg production can be facilitated, and warping of the resin substrate can be suppressed.

[0109] As the glass fiber substrate, for example, a glass fiber substrate formed of one or more types of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass is preferably used.

[0110] (Metal-clad laminate) In this embodiment, the metal-clad laminate is one in which a metal layer is disposed on at least one surface of the cured product of the prepreg. A method for manufacturing a metal-clad laminate using a prepreg is, for example, as follows.

[0111] Metal foil is placed on both or one of the outer surfaces of a prepreg or a laminate of two or more prepregs, and these are bonded under high vacuum conditions using a laminator or Becquerel apparatus, or metal foil is placed on both or one of the outer surfaces of the prepreg. When two or more prepregs are laminated, metal foil is placed on both or one of the outermost surfaces of the laminated prepregs. The laminate of prepregs and metal foil is then heated and pressurized to obtain a metal-clad laminate. It is preferable to continue pressing during the heating and pressurizing process until cooling is complete.

[0112] Examples of metals constituting the metal foil include copper, copper-based alloys, aluminum, aluminum-based alloys, silver, silver-based alloys, gold, gold-based alloys, zinc, zinc-based alloys, nickel, nickel-based alloys, tin, tin-based alloys, iron, iron-based alloys, Fe-Ni-based alloys such as Kovar (trade name), 42 alloy, Invar, and Super Invar, W, and Mo. Among these, copper or copper alloys are preferred as the metal constituting the metal foil 105 because they have excellent conductivity, are easy to form circuits by etching, and are inexpensive. That is, copper foil is preferred as the metal foil 105. As the metal foil, a metal foil with a carrier or the like can also be used. The thickness of the metal foil is preferably 0.5 μm or more and 20 μm or less, and more preferably 1.5 μm or more and 18 μm or less. According to this embodiment, by adopting such a resin film or a prepreg using the same, This makes it possible to configure an insulating layer in a printed wiring board with a reduced linear expansion coefficient in the planar direction.

[0113] (printed wiring board) The printed wiring board of this embodiment is provided with an insulating layer made of the cured product of the above-mentioned resin film (cured product of the thermosetting resin composition).

[0114] In this embodiment, the cured resin film can be used, for example, as a core layer, build-up layer, or solder resist layer of a normal printed wiring board, a build-up layer or solder resist layer of a printed wiring board having no core layer, an interlayer insulating layer or solder resist layer of a coreless substrate used in PLP, an interlayer insulating layer or solder resist layer of an MIS substrate, etc. Such insulating layers can also be suitably used as interlayer insulating layers or solder resist layers constituting large-area printed wiring boards used to collectively produce multiple semiconductor packages. Next, an example of the printed wiring board 300 of this embodiment will be described with reference to FIGS. 2(a) and 2(b).

[0115] The printed wiring board 300 of this embodiment includes an insulating layer formed from a cured product of the resin film 10. As shown in FIG. 2(a), the printed wiring board 300 may have a structure including an insulating layer 301 (core layer) and an insulating layer 401 (solder resist layer). Alternatively, as shown in FIG. 2(b), the printed wiring board 300 may have a structure including an insulating layer 301 (core layer), an insulating layer 305 (buildup layer), and an insulating layer 401 (solder resist layer). Each of the core layer, buildup layer, and solder resist layer may be formed from, for example, a cured product of the resin film of this embodiment. The core layer may be formed from a cured product obtained by curing a prepreg formed by impregnating a fiber substrate with the thermosetting resin composition of this embodiment.

[0116] The cured product of the resin film of this embodiment may not contain a fiber substrate such as glass cloth or a paper substrate, which makes it particularly suitable for forming a build-up layer (interlayer insulating layer) or a solder resist layer.

[0117] Furthermore, printed wiring board 300 according to this embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board. A double-sided printed wiring board is a printed wiring board in which metal layers 303 are laminated on both sides of insulating layer 301. A multilayer printed wiring board is a printed wiring board in which two or more build-up layers (e.g., insulating layer 305) are laminated on insulating layer 301, which is a core layer, by a plated-through-hole method, a build-up method, or the like.

[0118] In this embodiment, the via holes 307 may be either through holes or blind holes as long as they are holes for electrically connecting layers. The via holes 307 may be formed by embedding a metal. The embedded metal may have a structure covered with an electroless metal plating film 308.

[0119] In this embodiment, the metal layer 303 may be, for example, a circuit pattern or an electrode pad. The metal layer 303 may have a metal laminate structure of, for example, a metal foil 105 and an electrolytic metal plating layer 309.

[0120] Metal layer 303 is formed by a semi-additive process (SAP) method on, for example, chemically or plasma-treated metal foil 105 or on the surface of an insulating layer (e.g., insulating layer 301 or insulating layer 305) made of a cured resin film of this embodiment. For example, after applying electroless metal plating film 308 to metal foil 105 or insulating layers 301 and 305, non-circuit formation areas are protected with a plating resist, electrolytic metal plating layer 309 is formed by electrolytic plating, and metal layer 303 is formed by removing the plating resist and patterning electrolytic metal plating layer 309 by flash etching. Furthermore, printed wiring board 300 of this embodiment may be a resin board that does not contain glass fibers. For example, insulating layer 301, which is the core layer, may be configured not to contain glass fibers.

[0121] (Semiconductor Devices) 3(a) and 3(b) are cross-sectional views showing an example of the configuration of a semiconductor device 400. As shown in FIG.

[0122] The semiconductor device 400 of this embodiment can include a printed wiring board 300 and a semiconductor element mounted on a circuit layer of the printed wiring board 300 or embedded in the printed wiring board 300 .

[0123] For example, the semiconductor device 400 shown in Fig. 3(a) has a structure in which a semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in Fig. 3(a). On the other hand, the semiconductor device 400 shown in Fig. 3(b) has a structure in which the semiconductor element 407 is mounted on the circuit layer (metal layer 303) of the printed wiring board 300 shown in Fig. 3(b). The semiconductor element 407 is covered with an encapsulant layer 413. Such a semiconductor package may have a flip-chip structure in which the semiconductor element 407 is electrically connected to the printed wiring board 300 via solder bumps 410 and the metal layer 303.

[0124] In this embodiment, the structure of the semiconductor package is not limited to the above-mentioned flip-chip connection structure and may have various structures, for example, a fan-out structure. The insulating layer made of the cured resin film of this embodiment can suppress substrate warpage and substrate cracks in the manufacturing process of a semiconductor package having a fan-out structure.

[0125] Next, a description will be given of a modified example of the printed wiring board of this embodiment. Figure 4 is a cross-sectional view showing steps in an example of a manufacturing process for a printed wiring board 500. Figure 4(c) shows a printed wiring board 500 that does not have a core layer.

[0126] The printed wiring board 500 of this embodiment does not include a core layer having a fiber base material, and can be, for example, a coreless resin board composed of buildup layers and solder resist layers. These buildup layers and solder resist layers are preferably composed of insulating layers made of the cured resin film of this embodiment. For example, the printed wiring board 500 shown in FIG. 4(c) includes two buildup layers (insulating layers 540 and 550) and a solder resist layer (insulating layer 560). The buildup layer of the printed wiring board 500 may be a single layer, or may include two or more layers. The insulating layer made of the cured resin film of this embodiment has excellent toughness, and therefore, warping of the printed wiring board 500 and cracks during transportation can be suppressed.

[0127] 4(c) may be a circuit pattern or an electrode pad, and may be formed by the SAP method as described above. These metal layers 542, 552, 562 may be a single layer or multiple metal layers.

[0128] The printed wiring board 500 may have a large area on which multiple semiconductor elements can be mounted on a flat surface. This allows multiple semiconductor elements mounted on the printed wiring board 500 to be encapsulated together and then separated into individual pieces, thereby obtaining multiple semiconductor packages. The printed wiring board 500 may be a panel substrate having a substantially circular or rectangular shape.

[0129] The method for manufacturing the printed wiring board 500 is not particularly limited. For example, the printed wiring board 500 can be obtained by forming a buildup layer and a solder resist layer on a support substrate 510 and then peeling off the support substrate 510. Specifically, as shown in FIG. 4(a), a carrier foil 520 and a metal foil 530 (e.g., copper foil) are placed on a large-area support substrate 510 (e.g., a plate member made of SUS). At this time, an adhesive resin (not shown) can be placed between the support substrate 510 and the carrier foil 520. Next, a metal layer 542 is formed on the metal foil 530. This metal layer 542 is patterned by a conventional method such as the SAP method. Next, the carrier film-attached resin film is laminated by a heat and pressure molding method or the like, and the carrier substrate is peeled off from the carrier film-attached resin film. The resin film is then cured. This process is repeated three times to form two buildup layers and one solder resist layer. 4(b), the support substrate 510 is peeled off, and the metal foil 530 is removed by etching or the like.

[0130] As a result of the above, the printed wiring board 500 shown in FIG. 4(c) is obtained. Next, a modified example of the printed wiring board of this embodiment will be described. Fig. 5 is a cross-sectional view showing an example of the configuration of a printed wiring board 600.

[0131] The printed wiring board 600 shown in FIG. 5 may be formed of a coreless resin substrate 610 used in a PLP (panel level packaging) process. The PLP process can obtain a panel-sized package having an area larger than that of a wafer by utilizing, for example, a wiring board process. By using the PLP process, it is possible to efficiently improve the productivity of semiconductor packages compared to wafer level processes.

[0132] In this embodiment, the insulating layer 612 (interlayer insulating layer) and the insulating layers 630, 632 (solder resist layers) of the coreless resin substrate 610 may be formed of an insulating layer made of a cured resin film of this embodiment. The cured resin film of this embodiment has excellent toughness, so that warping of the printed wiring board 600 during the PLP process and cracks in the coreless resin substrate 610, particularly during transportation and mounting, can be effectively suppressed.

[0133] Furthermore, the printed wiring board 600 of this embodiment has a large area that allows multiple semiconductor elements (not shown) to be mounted within its plane. The multiple semiconductor elements mounted in the in-plane direction of the printed wiring board 600 are encapsulated together, and then the resulting encapsulated semiconductor elements are separated into individual pieces, thereby obtaining multiple semiconductor packages. Since the linear expansion coefficient of the cured resin film of this embodiment can be reduced, package warpage can be suppressed in semiconductor packages obtained by the PLP process.

[0134] The printed wiring board 600 may include a coreless resin substrate 610 and a solder resist layer (insulating layers 630, 632) formed on the surface thereof. The coreless resin substrate 610 may include an embedded semiconductor element 620. The semiconductor element 620 may be electrically connected via via wiring 616. The coreless resin substrate 610 may also include at least an insulating layer 612 (interlayer insulating layer) and via wiring 616. A metal layer 640 (electrode pad) on the lower surface and a metal layer 618 (post) on the upper surface may be electrically connected via the via wiring 616. The via wiring 616 may be connected to the metal layer 640 via a metal layer 614 (post). The via wiring 616 and the metal layer 614 are embedded in the coreless resin substrate 610. The surface of the metal layer 614, which is a post, may be flush with the surface of the coreless resin substrate 610. In the printed wiring board 600 of this embodiment, the coreless resin substrate 610 is configured with a single interlayer insulating layer, but is not limited to this configuration and may have a structure in which multiple interlayer insulating layers are stacked. At least via wiring 616 may be formed in such an interlayer insulating layer as an interlayer connection wiring. In this embodiment, the via wiring 616, the metal layer 614, or the metal layer 618 may be configured with a metal such as copper.

[0135] The upper and lower surfaces of the coreless resin substrate 610 may be covered with solder resist layers (insulating layers 630, 632). For example, the insulating layer 630 may cover a metal layer 650 formed on the surface of the insulating layer 612. The metal layer 650 is composed of a first metal layer 652 (plated layer) and a second metal layer 654 (electroless plated layer), and may be formed by, for example, the SAP method. The metal layer 650 may be, for example, a circuit pattern or an electrode pad.

[0136] Furthermore, the method for manufacturing the printed wiring board 600 of this embodiment is not particularly limited, but the following method can be used, for example. For example, an insulating layer 612 is formed on a support substrate. Next, vias are formed in the insulating layer 612, and via wiring 616 is formed by embedding a metal film in the vias by a plating method. Next, rewiring (metal layer 650) is formed on the surface of the insulating layer 612 by the SAP method. Thereafter, multiple interlayer insulating layers having such interlayer connection wiring may be laminated. Then, solder resist layers (insulating layers 630, 632) are formed. In this way, the printed wiring board 600 can be obtained.

[0137] Next, a modified example of the printed wiring board of this embodiment will be described.

[0138] 6 can be configured as a substrate with posts (MIS substrate). For example, the substrate with posts can be configured as a coreless resin substrate 710 having a structure in which via wiring 716 and a metal layer 718 (posts) are embedded in an insulating layer 712 (interlayer insulating layer). The substrate with posts can be a substrate after being divided into individual pieces, or a substrate having a large area before being divided into individual pieces (for example, a support such as a wafer).

[0139] By using the printed wiring board 700 of this embodiment, it is possible to efficiently improve the productivity of semiconductor packages to the same extent as or even better than wafer-level processes.

[0140] In this embodiment, the insulating layer 712 (interlayer insulating layer) and insulating layers 730, 732 (solder resist layers) of the coreless resin substrate 710 may be formed of an insulating layer made of a cured resin film of this embodiment. The cured resin film of this embodiment has excellent toughness, so that warping of the printed wiring board 700 and cracks in the coreless resin substrate 710, particularly during transportation and mounting, can be effectively suppressed.

[0141] Furthermore, the printed wiring board 700 of this embodiment has a large area that allows multiple semiconductor elements (not shown) to be mounted within its plane. The multiple semiconductor elements mounted in the in-plane direction of the printed wiring board 700 are encapsulated together, and then the resulting semiconductor packages can be obtained by dividing them into individual pieces. Since the linear expansion coefficient of the cured resin film of this embodiment can be reduced, package warpage can be suppressed in the resulting semiconductor packages.

[0142] The printed wiring board 700 may include a coreless resin substrate 710 and a solder resist layer (insulating layers 730, 732) formed on the surface thereof. The coreless resin substrate 710 may include an embedded semiconductor element 720. The semiconductor element 720 may be electrically connected via via wiring 716. The coreless resin substrate 710 may include at least an insulating layer 712 (interlayer insulating layer), via wiring 716, and a metal layer 718 (post). The metal layer 714 (post) on the lower surface and the metal layer 718 (post) on the upper surface may be electrically connected via the via wiring 716. The metal layer 714 embedded in the insulating layer 712 may be connected to a metal layer 740 (electrode pad) formed on the surface of the insulating layer 712. The surface of the insulating layer 712 may have a polished surface. One surface of the metal layer 718 may be flush with the polished surface of the insulating layer 712.

[0143] In the printed wiring board 700 of this embodiment, the coreless resin substrate 710 is configured with a single interlayer insulating layer, but is not limited to this configuration and may have a structure in which multiple interlayer insulating layers are stacked. Via wiring 716 and metal layer 718 (post) may be formed in such an interlayer insulating layer as interlayer connection wiring. In this embodiment, the via wiring 716, metal layer 714, or metal layer 718 may be configured with a metal such as copper. The upper and lower surfaces of the coreless resin substrate 710 may be covered with solder resist layers (insulating layers 730 and 732).

[0144] Furthermore, the method for manufacturing the printed wiring board 700 of this embodiment is not particularly limited, but the following method can be used, for example. For example, on a support substrate, copper posts (e.g., metal layer 718) are formed on an insulating layer. The copper posts are further embedded in an insulating layer. Next, the surfaces of the copper posts are exposed (i.e., the copper post heads are exposed) by a method such as grinding or chemical etching. Next, rewiring is formed by the SAP method. By these steps, a coreless resin substrate 710 having an interlayer insulating layer can be formed. Thereafter, by repeating the step of forming the interlayer insulating layer multiple times, multiple interlayer insulating layers having interlayer connection wiring may be stacked. Then, solder resist layers (insulating layers 730, 732) are formed. By the above steps, the printed wiring board 700 can be obtained.

[0145] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted as long as they do not impair the effects of the present invention. [Example]

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0147] [Synthesis Example 1] Norbornene (75% toluene solution) was replaced with butylnorbornene, and polymerization was carried out in the same manner as in Synthesis Example 3 under the conditions in Table 1 below. After completion of the reaction, 57 g of the reaction solution was diluted with 100 g of toluene and added dropwise to 200 g of methanol to cause reprecipitation. The precipitated polymer was collected by filtration, and the residue was washed with 200 g of methanol and separated by filtration. Finally, the mixture was dried in a vacuum at room temperature to obtain purified Polymer 1. The composition ratio of butylnorbornene and 5-vinyl-2-norbornene in the obtained polymer 1 was 1 The ratio was calculated to be 5:5 based on H-NMR measurement. The weight average molecular weight (Mw) of the obtained polymer 1 measured under the following conditions was 6,000, the number average molecular weight (Mn) was 2,500, and the molecular weight distribution (PDI: Mw / Mn) was 2.3. (Measurement conditions) The weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (PDI: Mw / Mn) of the obtained polymer 1 were determined using polystyrene-equivalent values obtained from a calibration curve of standard polystyrene (PS) obtained by GPC measurement under the following measurement conditions: Tosoh Corporation gel permeation chromatography device HLC-8320GPC Column: TSK-GEL Supermultipore HZ-M manufactured by Tosoh Corporation Detector: RI detector for liquid chromatography Measurement temperature: 40℃ Solvent: THF Sample concentration: 2.0 mg / ml

[0148] [Synthesis Example 2] Polymerization was carried out in the same manner as in Synthesis Example 3 using three monomers: norbornene, 5-vinyl-2-norbornene, and phenylethylnorbornene, under the conditions shown in Table 1 below. After the reaction was completed, 66 g of the reaction solution was added dropwise to 480 g of methanol to cause reprecipitation. The precipitated polymer was separated by filtration, air-dried, and then dissolved in 60 g of toluene and 110 g of THF. The dissolved liquid was added dropwise to 1,070 g of methanol to cause reprecipitation again, and the solution was separated by filtration. Finally, the polymer was dried under vacuum at room temperature to obtain purified Polymer 2. The composition ratio of norbornene, phenylethylnorbornene, and 5-vinyl-2-norbornene in the obtained polymer 2 was 1 The ratio was calculated to be 3:1:1 by H-NMR measurement. The weight average molecular weight (Mw) of the obtained polymer 2 measured under the above conditions was 2,700, the number average molecular weight (Mn) was 1,400, and the molecular weight distribution (PDI: Mw / Mn) was 2.0.

[0149] [Synthesis Example 3] A reaction solution was obtained by adding norbornene (75% concentration toluene solution), 5-vinyl-2-norbornene, triethylsilane, 1-butanol, and anisole to a three-neck flask in the weight ratios shown in Table 1 below. After bubbling nitrogen through the reaction solution, it was heated to 75°C. A catalyst (palladium(II)(acetonitrile)bis(triisopropylphosphine)acetate tetrakis(2,3,4,5,6-pentafluorophenyl)borate, Pd-1206) and a cocatalyst (N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, DANFABA) were dissolved in a toluene:ethyl acetate = 6:4 solution, and added to the reaction solution so that the total amount of norbornene monomer:catalyst:cocatalyst = 20,000:1:1 (molar ratio). Polymerization was then carried out by heating at the reaction temperature and for the time listed in Table 1 below. After polymerization was completed, the reaction was stopped by allowing to cool. After the reaction was completed, 110 g of the reaction mixture was dropped into a mixture of 500 g of methanol and 150 g of THF to reprecipitate. The polymer was recovered by filtration, and then washed with a mixture of 100 g of methanol and 100 g of THF and filtered. Finally, the mixture was vacuum dried at 80°C to obtain purified polymer 3. The weight average molecular weight (Mw) of the obtained polymer 3 measured under the above conditions was 2,200, the number average molecular weight (Mn) was 1,000, and the molecular weight distribution (PDI:Mw / Mn) was 2.2.

[0150] [Synthesis Example 4] Polymerization was carried out in the same manner as in Synthesis Example 3, except that 5-vinyl-2-norbornene was replaced with butenylnorbornene under the conditions shown in Table 1 below. After the reaction was completed, 68 g of the reaction solution was added dropwise to 510 g of methanol to cause reprecipitation. The precipitated polymer was separated by filtration, air-dried, and then dissolved in 40 g of THF. The dissolved liquid was added dropwise to 430 g of methanol to cause reprecipitation again, and the solution was separated by filtration. Finally, the polymer was dried in a vacuum at room temperature to obtain purified Polymer 4. The composition ratio of norbornene to butenylnorbornene in the obtained polymer 4 was 1 The ratio was calculated to be 3:1 by H-NMR measurement. The weight average molecular weight (Mw) of the obtained polymer 4 measured under the above conditions was 2,700, the number average molecular weight (Mn) was 1,300, and the molecular weight distribution (PDI:Mw / Mn) was 2.2.

[0151] [Synthesis Example 5] Polymerization was carried out in the same manner as in Synthesis Example 3, except that 5-vinyl-2-norbornene was replaced with hexenylnorbornene under the conditions shown in Table 1 below. After the reaction was completed, 113 g of the reaction solution was added dropwise to 850 g of methanol to cause reprecipitation. The precipitated polymer was separated by filtration, air-dried, and then dissolved in 90 g of toluene and 180 g of THF. The dissolved liquid was added dropwise to 2450 g of methanol to cause reprecipitation again, and the solution was separated by filtration. Finally, the polymer was dried in a vacuum at room temperature to obtain purified Polymer 5. The composition ratio of norbornene to hexenylnorbornene in the obtained polymer 5 was 1 The ratio was calculated to be 3:1 by H-NMR measurement. The weight average molecular weight (Mw) of the obtained polymer 5 measured under the above conditions was 3,100, the number average molecular weight (Mn) was 1,500, and the molecular weight distribution (PDI:Mw / Mn) was 2.0.

[0152] [Synthesis Example 6] Polymerization was carried out in the same manner as in Synthesis Example 3 under the conditions shown in Table 1 below. After the reaction was completed, 580 g of the reaction solution was added dropwise to 1400 g of methanol to cause reprecipitation. The precipitated polymer was separated by filtration, air-dried, and then dissolved in 350 g of toluene. The dissolved liquid was added dropwise to a mixture of 1800 g of methanol and 360 g of THF to cause reprecipitation again, and the polymer was separated by filtration. Finally, the polymer was dried in a vacuum at 80°C to obtain purified Polymer 6.

[0153] [Table 1]

[0154] The components used in preparing the thermosetting resin composition are listed below. (thermosetting resin) Polymer 1: Polymer obtained in Synthesis Example 1 Polymer 2: Polymer obtained in Synthesis Example 2 Polymer 3: Polymer obtained in Synthesis Example 3 Polymer 4: Polymer obtained in Synthesis Example 4 Polymer 5: Polymer obtained in Synthesis Example 5

[0155] (epoxy resin) Epoxy resin 1: Naphthalene-modified cresol novolac epoxy resin (product name: EXA-7320, manufactured by DIC Corporation)

[0156] (cyanate resin) Cyanate resin 1: Phenol novolac cyanate resin (product name: PT-30, manufactured by Lonza Japan)

[0157] (Crosslinking agent: liquid at room temperature (25°C)) Crosslinking agent 1: triallyl isocyanurate (number average molecular weight: 249, product name: TAIC, manufactured by Mitsubishi Chemical Corporation) Crosslinking agent 2: Polybutadiene (number average molecular weight: 1200, product name: B-1000, manufactured by Nippon Petrochemical Co., Ltd.) Crosslinker 3: Styrene-butadiene rubber (styrene content: 25% by mass, number average molecular weight: 4500, product name: Ricon 100, manufactured by Cray Valley)

[0158] (Crosslinking agent: solid at room temperature (25°C)) Crosslinker 4: Terminal methacrylic group-modified polyphenylene ether (number average molecular weight: 1,700, product name: SA-9000, manufactured by SABIC Innovative Plastics Japan, LLC) Crosslinking agent 5: styrene-modified polyphenylene ether (number average molecular weight: 2,200, product name: OPE-2st-2200, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0159] (Radical polymerization initiator) Radical polymerization initiator 1: bis(t-butylperoxy)diisopropylbenzene (product name: Perbutyl P, manufactured by NOF Corporation)

[0160] (curing accelerator) Curing accelerator 1: 2-phenyl-4-methylimidazole (product name: 2P4MZ, manufactured by Shikoku Chemical Industries, Ltd.)

[0161] (Silica filler) Silica filler 1: Admatechs, SC4050, particle size 1.1 μm

[0162] [Examples 1 to 10, Comparative Example 1] Each component shown in Table 2 was dissolved or dispersed, and the nonvolatile content was adjusted to 60% by mass with toluene, followed by stirring using a high-speed stirrer to prepare a varnish-like thermosetting resin composition. The prepared thermosetting resin composition was applied to a polyimide film and dried to obtain a 100 μm resin film. A polyimide film was placed on top of the resin film, and vacuum pressing was performed under reduced pressure at 200 to 225°C for 90 minutes at a pressure of 0.2 MPa. After cooling to room temperature, the cured film was peeled off from the polyimide film to prepare a test specimen. The dielectric properties (dielectric constant, dielectric loss tangent) and glass transition temperature of the obtained resin plate were measured by the following measuring methods. The results are shown in Table 1.

[0163] <Measurement of dielectric properties (relative permittivity, dielectric loss tangent) using the cavity resonator method> The resin plates obtained in the examples were cooled to room temperature, and then the cured film was peeled off from the polyimide film to prepare test specimens. The test pieces were pretreated by placing them in an environment of 22±1°C and 60±5% RH for 12 hours. The measurement equipment used was a network analyzer HP8510C, a synthesized sweeper HP83651A, and a test set HP8517B (all manufactured by Agilent Technologies). The dimensions of the cylindrical cavity resonator were an inner diameter of 42 mm and a height of 30 mm. When the sample was not inserted into the resonator, the TE 011 The mode is designed to be around 10 GHz. The resonant frequency, 3 dB bandwidth, transmitted power ratio, etc. were measured with and without a test piece inserted in the resonator. These measurement results were then analytically calculated using software to determine dielectric properties such as the dielectric loss tangent. The measurement mode was TE 011 Mode.

[0164] <Glass transition temperature> The test pieces were subjected to dynamic viscoelasticity measurement using a DMA device (Q800 manufactured by TA Instruments) at a temperature rise rate of 5°C / min and a frequency of 1 Hz. The glass transition temperature was determined as the temperature at which the loss tangent tanδ was maximized.

[0165] [Table 2]

[0166] As shown in Table 2, the thermosetting resin compositions according to the present invention obtained in the examples were able to give cured products that had excellent heat resistance, low dielectric constants and dielectric loss tangents, and excellent dielectric properties. In other words, the thermosetting resin compositions according to the present invention were able to give cured products that had an excellent balance of these properties.

[0167] [Example 11] Each component shown in Table 3 was dissolved or dispersed, and the nonvolatile content was adjusted to 60% by mass with toluene. The mixture was stirred using a high-speed stirrer to prepare a varnish-like thermosetting resin composition. The prepared thermosetting resin composition was applied to copper foil and dried to obtain a 30 μm resin film. A glass cloth was sandwiched between two resin films and vacuum pressed at 225°C for 90 minutes under reduced pressure and a pressure of 3 MPa. The obtained substrate was etched to remove the copper foil, and this was used as a test piece for dielectric constant measurement. The dielectric properties (dielectric constant, dielectric loss tangent) and glass transition temperature of the obtained test piece were measured by the above-mentioned measuring methods. The results are shown in Table 3.

[0168] [Table 3]

[0169] As shown in Table 3, the thermosetting resin composition containing the filler according to the present invention obtained in Example 11 was able to give a cured product that had excellent heat resistance, low dielectric constant and dielectric loss tangent, and excellent dielectric properties. In other words, the thermosetting resin composition according to the present invention was able to give a cured product that had an excellent balance of these properties. [Explanation of symbols]

[0170] 10 Resin film 12 Carrier substrate 100 Resin film with carrier 105 Metal foil 300 Printed Wiring Board 301 Insulation layer 303 Metal layer 305 Insulation Layer 307 Beer Hall 308 Electroless metal plating film 309 Electrolytic metal plating layer 400 Semiconductor Devices 401 Insulating layer 407 Semiconductor elements 410 Solder Bump 413 Encapsulant layer 500 Printed Wiring Board 510 Support substrate 520 Carrier Foil 530 Metal foil 540 Insulating Layer 542 Metal layer 550 insulating layer 552 Metal layer 560 Insulating Layer 562 Metal layer 600 Printed Wiring Board 610 Coreless Resin Substrate 612 Insulating layer 614 Metal layer 616 Via Wiring 618 Metal layer 620 Semiconductor elements 630 Insulating layer 632 Insulating layer 640 Metal layer 650 metal layer 652 1st metal layer 654 2nd metal layer 700 Printed Wiring Board 710 Coreless Resin Substrate 712 Insulation Layer 714 Metal layer 716 Via Wiring 718 Metal layer 720 Semiconductor elements 730 Insulation Layer 732 Insulation Layer 740 Metal layer

Claims

1. (A) a thermosetting resin; (B) a crosslinking agent; Including, The thermosetting resin (A) is A structural unit a represented by the following general formula (1), A structural unit b represented by the following general formula (2), and having a weight average molecular weight of 500 or more and 10,000 or less, The thermosetting resin (A) does not contain a structural unit derived from ethylene or an α-olefin, The crosslinking agent (B) is a thermosetting resin composition (excluding the case where the composition contains a fluorine-containing polymer composed of polymerization units derived from a fluorine-containing monomer and polymerization units derived from a norbornene monomer having two or more carbon-carbon double bonds), the thermosetting resin composition comprising a crosslinking agent (b1) that is liquid at room temperature (25°C) and a crosslinking agent (b2) that is solid at room temperature (25°C). 【Chemical 1】 (In general formula (1), R １ , R ２ , R ３ and R ４ each independently represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms (excluding groups having a terminal double bond); and n is 0, 1, or 2. 【Chemistry 2】 (In the general formula (2), Q represents a group having a terminal double bond, and R １ , R ２ , and R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; and m is 0, 1, or 2.

2. 2. The thermosetting resin composition according to claim 1, wherein the total amount of the structural units a and b in the thermosetting resin (A) is 80 mol % or more of all structural units.

3. 3. The thermosetting resin composition according to claim 1, wherein the group having a terminal double bond in Q of the general formula (2) includes a vinyl group, an allyl group, a (meth)acryloyl group, a vinylphenyl group, or a maleimide group.

4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the crosslinking agent (b1) comprises a crosslinking agent having two or more reactive groups.

5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the crosslinking agent (b2) includes a crosslinking agent having a weight average molecular weight of 1,000 or more and 20,000 or less.

6. The thermosetting resin composition according to any one of claims 1 to 5, further comprising a radical polymerization initiator (C).

7. The thermosetting resin composition according to any one of claims 1 to 6, further comprising a filler (D).

8. 8. The thermosetting resin composition according to claim 1, which is used to form a resin film with a carrier, the resin film comprising a carrier base material and a resin film provided on at least one side of the carrier base material.

9. The thermosetting resin composition according to any one of claims 1 to 7, which is used to form a resin layer in a prepreg containing a fiber base material in the resin layer.

10. The thermosetting resin composition according to claim 9 , wherein the fibrous substrate comprises glass cloth.

11. A carrier substrate; A resin film with a carrier, comprising: a resin film formed on the carrier substrate and made of the thermosetting resin composition according to any one of claims 1 to 7.

12. A prepreg comprising a fiber substrate in a resin layer made of the thermosetting resin composition according to any one of claims 1 to 7.

13. A laminate comprising the prepreg according to claim 12 and a metal layer disposed on at least one surface thereof.

14. A printed wiring board comprising an insulating layer made of a cured product of the thermosetting resin composition according to any one of claims 1 to 7.

15. The printed wiring board according to claim 14; a semiconductor element mounted on a circuit layer of the printed wiring board or embedded in the printed wiring board.

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