Resin composition

Abstract

To provide a resin composition and the like capable of forming a cured product excellent in dielectric properties, elongation, and adhesion before and after a HAST test. The solution to the above problem is a resin composition comprising: (A) a polyimide resin containing either of a dimer diamine skeleton and a trimer triamine skeleton, and a fluorene skeleton, and (B) a thermosetting resin.

Description

Technical Field

[0001] This invention relates to resin compositions, resin sheets, circuit boards, and semiconductor devices. Background Technology

[0002] Printed wiring boards and other circuit boards are widely used in various electronic instruments. As a method for manufacturing circuit boards, a layer-addition method is known that involves alternately stacking insulating and conductive layers on an inner substrate. The insulating layer is formed, for example, by curing a resin composition (Patent Documents 1 and 2). Specifically, it is known to form a resin composition layer containing a resin composition and then cure the resin composition layer, thereby forming an insulating layer containing a cured resin composition.

[0003] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2022-100697 Patent document 2: Japanese Patent Application Publication No. 2023-037522. Summary of the Invention

[0004] The problem that the invention aims to solve In recent years, with the increasing functionality of circuit boards, there is a demand for reducing the dielectric constant and dielectric loss tangent of the insulating layer. However, reducing the dielectric constant and dielectric loss tangent can sometimes lead to cracking after TCT (Thermal Cycle Test). Therefore, insulating layers with excellent elongation are required. Furthermore, reducing the dielectric constant and dielectric loss tangent can result in a time lag between the insulating layer and the conductor layer before and after the HAST test. Sometimes, the dielectric constant and dielectric loss tangent are collectively referred to as dielectric properties.

[0005] The present invention was created in view of the aforementioned problems, and its object is to provide: a resin composition capable of forming a cured product with excellent dielectric properties, elongation and adhesion before and after HAST testing; a resin sheet containing the resin composition; a cured product of the resin composition; a circuit board containing the cured product of the resin composition; and a semiconductor device containing the aforementioned circuit board.

[0006] Methods for solving problems In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that by combining a specific polyimide resin and a thermosetting resin, the above-mentioned problems can be solved, thus completing the present invention.

[0007] That is, the present invention includes the following.

[0008] [1] A resin composition comprising: (A) A polyimide resin comprising either a dimericane backbone or a melamine backbone, and a fluorene backbone, and (B) Thermosetting resins.

[0009] [2] The resin composition according to [1], wherein the end of component (A) has a maleimide group.

[0010] [3] The resin composition according to [1] or [2], wherein component (A) further comprises an anhydride skeleton.

[0011] [4] The resin composition according to [3], wherein the anhydride skeleton comprises a skeleton derived from bisphenol A type dianhydride.

[0012] [5] The resin composition according to any one of [1] to [4], wherein component (B) has any one of the functional groups of epoxy group, maleimide group and styrene group.

[0013] [6] The resin composition according to any one of [1] to [5], wherein when the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) is 0.01% by mass or more and 10% by mass or less.

[0014] [7] The resin composition according to any one of [1] to [6], wherein when the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is 5% by mass or more and 40% by mass or less.

[0015] [8] The resin composition according to any one of [1] to [7] further comprises (C) an inorganic filler material.

[0016] [9] According to the resin composition of [8], when the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 50% by mass or more and 90% by mass or less.

[0017]

[10] The resin composition according to any one of [1] to [9], wherein the mass ratio of component (B) to component (A), i.e., component (B) / (A) is 5 or more.

[0018]

[11] A resin sheet comprising a support and a resin composition layer comprising any one of the resin compositions described in [1] to

[10] disposed on the support.

[0019]

[12] A circuit board comprising an insulating layer formed from a cured resin composition of any one of [1] to

[10] .

[0020]

[13] A semiconductor device comprising the circuit board described in

[12] .

[0021] Invention Effects According to the present invention, a resin composition capable of forming a cured product with excellent dielectric properties, elongation and adhesion before and after HAST testing can be provided; a resin sheet comprising the resin composition; a cured product of the resin composition; a circuit board comprising the cured product of the resin composition; and a semiconductor device comprising the aforementioned circuit board. Detailed Implementation

[0022] The present invention will now be described with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented in different ways without departing from the scope of the claims and their equivalents.

[0023] [Resin Composition] The resin composition comprises: (A) a polyimide resin comprising either a dimericane backbone or a melamine backbone, and a fluorene backbone (hereinafter, sometimes referred to as "(A) polyimide resin"), and (B) a thermosetting resin. In this invention, by combining components (A) and (B), cured products with excellent dielectric properties, elongation, and adhesion before and after HAST testing can be obtained. Furthermore, cured products with high glass transition temperatures and low coefficients of linear thermal expansion (CTE) can generally also be obtained.

[0024] The resin composition may further comprise any other components in combination with components (A) to (B). Examples of such other components include, for example, (C) an inorganic filler, (D) a thermoplastic resin, (E) an organic filler, (F) a curing accelerator, (G) any additives, and (H) a solvent. The components contained in the resin composition will be described in detail below.

[0025] <(A) Polyimide Resin> The resin composition comprises (A) a polyimide resin containing either a dimeric diamine backbone or a melamine backbone, and a fluorene backbone. Component (A) can be used alone or in combination of two or more. By including component (A) in the resin composition, the elongation and adhesion before and after the HAST test are excellent. As component (A), by introducing either a highly flexible dimeric diamine backbone or a melamine backbone, and a large-volume fluorene backbone, the free volume increases, molecular mobility increases, and the anchoring effect is more favorable. Therefore, it is believed that a resin composition with excellent elongation and adhesion before and after the HAST test can be obtained.

[0026] As component (A), there are no particular limitations as long as it is a polyimide resin containing either a dimericane backbone or a melamine backbone, and a fluorene backbone.

[0027] The dimeric diamine skeleton refers to the skeleton of a dimeric diamine compound obtained by replacing the two terminal carboxylic acid groups (-COOH) of a dimer acid with aminomethyl (-CH2-NH2) or amino (-NH2).

[0028] Dimer acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids with 11 to 22 carbon atoms, particularly preferably unsaturated fatty acids with 18 carbon atoms), and their industrial manufacturing methods are basically standardized in the industry. Dimer acids can be readily obtained that are primarily composed of 36-carbon dimers obtained by dimerizing particularly inexpensive and readily available 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid. Furthermore, while double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrides that undergo further hydrogenation to reduce the degree of unsaturation are also included in the dimer acids.

[0029] The number of carbon atoms per molecule of the dimeramine compound is preferably 15 or more, more preferably 20 or more, further preferably 25 or more, more preferably 50 or less, more preferably 45 or less, and even more preferably 40 or less. Furthermore, the aliphatic group contained in the dimeramine compound can be a saturated aliphatic group or an unsaturated aliphatic group. In addition, the dimeramine backbone may also have carbon-carbon unsaturated bonds. The number of carbon-carbon unsaturated bonds in each dimeramine backbone is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0.

[0030] Dimeric diamine compounds typically comprise a backbone consisting of an aliphatic hydrocarbon group linked to two amino groups, and side chains consisting of two aliphatic hydrocarbon groups bonded to the backbone. The aliphatic hydrocarbon groups constituting the backbone can be aliphatic hydrocarbon groups with a cyclic structure. Therefore, the dimeric diamine backbone typically contains rings in its molecular structure, and each dimeric diamine backbone comprises two side chains consisting of aliphatic hydrocarbon groups. The aliphatic hydrocarbon groups serving as side chains are preferably unbranched, straight-chain aliphatic hydrocarbon groups. Furthermore, from the viewpoint of significantly obtaining the desired effects of the present invention, the number of carbon atoms in each aliphatic hydrocarbon group serving as a side chain is preferably 2 or more, preferably 20 or less, more preferably 19 or less, and even more preferably 18 or less. Further, from the viewpoint of significantly obtaining the desired effects of the present invention, of the two side chains in each dimeric diamine backbone, preferably one or more side chains are saturated aliphatic hydrocarbon groups, and particularly preferably all side chains are saturated aliphatic hydrocarbon groups.

[0031] As one embodiment, the dimeric diamine compound is preferably any one of the following: the compound shown in formula (a), the compound shown in formula (b), the compound shown in formula (c), and the compound shown in formula (d).

[0032] [Chemistry 1] In the formula, m, n, p, and q represent integers greater than 1 chosen in the order m + n = 6 to 17 and p + q = 8 to 19, respectively. The bonds shown by the dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds. When the bonds shown by the dashed lines are carbon-carbon double bonds, formulas (a) and (b) become structures obtained by subtracting the number of hydrogen atoms bonded to each carbon atom constituting the carbon-carbon double bond from the numbers shown in formulas (a) and (b).

[0033] Dimeric diamine compounds can be manufactured, for example, by reductively amination of unsaturated fatty acids such as dimer acids or their esters, higher unsaturated nitriles or higher unsaturated alcohols, followed by dimerization. Alternatively, dimeric diamines can be manufactured, for example, by dimerizing the aforementioned unsaturated fatty acids or their esters, higher unsaturated nitriles or higher unsaturated alcohols to obtain polybasic fatty acids, polybasic nitriles or polyols, followed by reductive amination. Furthermore, the method for manufacturing dimeric diamines may also include performing a hydrogenation reaction. The method for manufacturing dimeric diamines can be found in Japanese Patent Application Publication No. 9-12712.

[0034] Dimeric diamine compounds can be commercially available. Examples of commercially available products include "PRIAMINE1073", "PRIAMINE1074", and "PRIAMINE1075" manufactured by Croda Japan; and "Versamine551" and "Versamine 552" manufactured by Kognis Japan.

[0035] The melamine backbone refers to the backbone of a melamine compound obtained by replacing the three terminal carboxylic acid groups (-COOH) from a trimeric acid with aminomethyl (-CH2-NH2) or amino (-NH2). Melamine compounds are usually byproducts of the manufacture of dimeric diamine compounds. Therefore, as component (A), it may contain both a dimeric diamine backbone and a melamine backbone, or it may contain only a dimeric diamine backbone.

[0036] Trimeric acid can be a byproduct of the manufacture of dimeric acid, and is a compound obtained by trimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly those with 18 carbon atoms).

[0037] The number of carbon atoms per molecule of the melamine compound is preferably 15 or more, more preferably 20 or more, further preferably 25 or more, more preferably 50 or less, more preferably 45 or less, and further preferably 40 or less. Furthermore, the aliphatic groups contained in the dimelamine compound can be saturated aliphatic groups or unsaturated aliphatic groups. In addition, the dimelamine backbone may also have carbon-carbon unsaturated bonds. The number of carbon-carbon unsaturated bonds in each dimelamine backbone is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0.

[0038] Melamine compounds typically comprise a backbone consisting of an aliphatic hydrocarbon group linked to three amino groups, and side chains consisting of three aliphatic hydrocarbon groups bonded to the backbone. The aliphatic hydrocarbon groups constituting the backbone can be aliphatic hydrocarbon groups with a cyclic structure. Therefore, the dimeramine backbone typically contains rings in its molecular structure, and each dimeramine backbone comprises three side chains consisting of aliphatic hydrocarbon groups. The aliphatic hydrocarbon groups serving as side chains are preferably unbranched, straight-chain aliphatic hydrocarbon groups. Furthermore, from the viewpoint of significantly obtaining the desired effects of the present invention, the number of carbon atoms in each aliphatic hydrocarbon group serving as a side chain is preferably 2 or more, preferably 20 or less, more preferably 19 or less, and even more preferably 18 or less. Further, from the viewpoint of significantly obtaining the desired effects of the present invention, of the three side chains in each melamine backbone, preferably one or more side chains are saturated aliphatic hydrocarbon groups, and particularly preferably all side chains are saturated aliphatic hydrocarbon groups.

[0039] The fluorene skeleton refers to the skeleton of a compound obtained by substituting either fluorene or 9,9-biphenylfluorene with an aminomethyl or amino group. The fluorene skeleton is preferably derived from fluorene diamine compounds obtained by substituting 9,9-biphenylfluorene with an aminomethyl or amino group.

[0040] From the viewpoint of significantly obtaining the effects of the present invention, the terminal of component (A) is preferably a maleimide group, and more preferably both terminals are maleimide groups. That is, from the viewpoint of significantly obtaining the effects of the present invention, component (A) preferably has at least a maleimide group. The maleimide group refers to 2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl.

[0041] It should be noted that component (A) may or may not contain polyimide resin without maleimide groups. That is, polyimide resin without maleimide groups may also be removed from component (A).

[0042] As component (A), in addition to either the skeleton of the dimeric diamine compound and the melamine compound, and the fluorene skeleton, it is preferred to further include an acid anhydride skeleton.

[0043] An anhydride skeleton refers to the skeleton derived from the anhydride. Tetracarboxylic anhydride is preferred as an acid anhydride. Examples of tetracarboxylic anhydrides include aromatic tetracarboxylic dianhydrides and aliphatic tetracarboxylic dianhydrides, with aromatic tetracarboxylic dianhydrides being preferred. Examples of aromatic tetracarboxylic dianhydrides include benzoyltetracarboxylic dianhydrides, naphthalenetetracarboxylic dianhydrides, anthracenetetracarboxylic dianhydrides, and bis(phthalic acid) dianhydrides, with bis(phthalic acid) dianhydrides being preferred. Examples of bis(phthalic acid) dianhydrides include bisphenol A type dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3 3',4'-Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-Diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-Diphenyl sulfone tetracarboxylic dianhydride, 2,2'-Bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 4,4'-Oxybisphthalic anhydride, Methylene-4,4'-bisphthalic dianhydride, 1,1-ethynyl-4,4'-bisphthalic dianhydride, 2,2-propylidene -4,4'-Diphthalic dianhydride, 1,2-Ethylene-4,4'-Diphthalic dianhydride, 1,3-Trimethylene-4,4'-Diphthalic dianhydride, 1,4-Tetramethylene-4,4'-Diphthalic dianhydride, 1,5-Pentamethylene-4,4'-Diphthalic dianhydride, 1,3-Bis(3,4-dicarboxyphenyl)phthalic dianhydride, 1,4-Bis(3,4-dicarboxyphenyl) Phthalic dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride, etc., wherein, as a bisphthalic dianhydride, bisphenol A type acid dianhydride is preferred. Examples of bisphenol A type acid dianhydride include, for example, 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride. Therefore, as the acid anhydride skeleton, bisphthalic dianhydride is preferred, more preferably a skeleton derived from bisphenol A type acid dianhydride, and even more preferably a skeleton derived from 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride.

[0044] In component (A), the ratio of the dimeric diamine backbone to the anhydride backbone (moles of anhydride backbone / moles of dimeric diamine backbone) is arbitrary as long as it does not impair the effects of the present invention. Specifically, it is preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. By keeping the aforementioned ratio within the aforementioned range, the desired effects of the present invention can be significantly obtained. Generally, the ratio of the dimeric diamine backbone to the anhydride backbone in component (A) is the same as the addition ratio of the dimeric diamine compound and the anhydride used as raw materials for manufacturing component (A).

[0045] In component (A), the ratio of the fluorene skeleton to the anhydride skeleton (moles of anhydride skeleton / moles of fluorene) is arbitrary as long as it does not impair the effects of the present invention. Specifically, it is preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. By keeping the aforementioned ratio within the aforementioned range, the desired effects of the present invention can be significantly obtained. Generally, the ratio of the fluorene skeleton to the anhydride skeleton in component (A) is the same as the addition ratio of the fluorene compound and the anhydride used as raw materials for manufacturing component (A).

[0046] In component (A), the ratio of the dimeramine backbone to the fluorene backbone (moles of fluorene backbone / moles of dimeramine backbone) is arbitrary as long as it does not impair the effects of the present invention. Specifically, it is preferably 0.3 or more, more preferably 0.5 or more, further preferably 1 or more, preferably 3 or less, more preferably 2 or less, and further preferably 1 or less. By keeping the aforementioned ratio within the aforementioned range, the desired effects of the present invention can be significantly obtained. Generally, the ratio of the dimeramine backbone to the fluorene backbone in component (A) is the same as the addition ratio of the dimeramine compound and the fluorene compound used as raw materials for manufacturing component (A).

[0047] Trimelamine compounds are usually byproducts of the manufacture of dimelamine compounds. Therefore, component (A) may contain both a dimelamine backbone and a melamine backbone.

[0048] In component (A), the ratio of the melamine backbone to the anhydride backbone (moles of anhydride backbone / moles of melamine backbone) is arbitrary as long as it does not impair the effect of the present invention. Generally, the ratio of the melamine backbone to the anhydride backbone in component (A) is the same as the addition ratio of the melamine compound and the anhydride used as raw materials for manufacturing component (A).

[0049] In component (A), the ratio of the melamine backbone to the fluorene backbone (moles of fluorene backbone / moles of melamine backbone) is arbitrary as long as it does not impair the effects of the present invention. Generally, the ratio of the melamine backbone to the fluorene backbone in component (A) is the same as the addition ratio of the melamine compound and the fluorene compound used as raw materials for manufacturing component (A).

[0050] In addition to any of the dimeric diamine and melamine skeletons, the fluorene skeleton, and the anhydride skeleton, component (A) may also contain any structural units as needed.

[0051] (A) The preferred component is any of the resins shown in formulas (A-1) to (A-4) below.

[0052] [Chemistry 2] In formulas (A-1) to (A-4), A 1 Each independently represents a divalent group having a fluorene skeleton, A 2 Each of the divalent groups represented independently by formula (1), A 3 Each of these groups independently represents a divalent group having a dimeric diamine backbone or a trimeric triamine backbone. n1, n2, n3, n4, n5, n6, n7, and n8 each independently represent an integer from 0 to 10.

[0053] In formula (1), X represents a tetravalent organic group independently, and * represents a bond.

[0054] In formulas (A-1) to (A-4), A 1 Each of these groups independently represents a divalent group having a fluorene skeleton. The fluorene skeleton is as described above. Examples of divalent groups having a fluorene skeleton include those shown in formulas (A1-1) to (A1-2) below, with the group shown in formula (A1-1) being preferred. In the formula, * represents a bond.

[0055] [Chemistry 3] In formulas (A-1) to (A-4), A 3 Each of these groups independently represents a divalent group having a dimeric diamine backbone or a trimeric triamine backbone, preferably a divalent group having a dimeric diamine backbone. The dimeric diamine backbone and the trimeric triamine backbone are as described above.

[0056] Examples of divalent groups having a dimeric diamine backbone include those shown in formulas (A3-1) to (A3-4) below. In these formulas, * denotes a bond.

[0057] [Chemistry 4] In formulas (A-1) to (A-4), A 2 Each of the divalent groups represented by formula (1) is independently represented, and in formula (1), X independently represents a tetravalent organic group. The divalent group represented by formula (1) has an anhydride skeleton. The anhydride skeleton is as described above. X preferably represents a tetravalent organic group containing two or more aromatic or aliphatic rings, and more preferably represents a tetravalent organic group containing an aromatic ring. The aromatic or aliphatic ring is a concept that includes a monocyclic or fused ring. Examples of tetravalent organic groups containing two or more aromatic or aliphatic rings include groups (a1) to (a10) below, preferably the group (a1) (a tetravalent group derived from 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic anhydride).

[0058] [Chemistry 5] In formulas (A-1) to (A-4), n1, n2, n3, n4, n5, n6, n7, and n8 each independently represent an integer from 0 to 10, preferably an integer from 0 to 5, more preferably an integer from 0 to 4, and even more preferably 1 to 3. When n1 is 0, n2 is preferably other than 0; when n3 is 0, n4 is preferably other than 0; when n5 is 0, n6 is preferably other than 0; and when n7 is 0, n8 is preferably other than 0.

[0059] Specific examples of component (A) include the resins shown in formulas (A4-1) to (A4-2) below. However, component (A) is not limited to these specific examples. In formula (A4-2), X is independently a divalent group having a dimericane backbone from a dimericane compound, as shown in any of formulas (a') to (d') below, where m ≥ 0 and n ≥ 1. In formulas (a') to (d'), * denotes a bond, and the bonds m, n, p, q, and those shown by dashed lines are the same as those shown by dashed lines in formulas (a) to (d).

[0060] [Chemistry 6] .

[0061] Component (A) is obtained by an imidization reaction in which an acid anhydride is reacted with any one of a dimeric diamine compound and a melamine compound, as well as a fluorene diamine compound. For example, Japanese Patent No. 5534378 may be referred to as a method for manufacturing component (A).

[0062] (A) can be a commercially available product. Examples of commercially available products that can be used as ingredient (A) include "BMI-4200" manufactured by Designer Molecules Inc. and "SLK-2800" manufactured by Shin-Etsu Chemical Co., Ltd.

[0063] The weight-average molecular weight of component (A) is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. Here, the weight-average molecular weight of component (A) is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0064] When the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, or 0.3% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, even more preferably 5% by mass or less, less than 5% by mass, 4% by mass or less, or 3.5% by mass or less.

[0065] In another embodiment, when the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) can be 0.4% by mass or more, 0.5% by mass or more, 0.6% by mass or more, 0.8% by mass or more, 0.9% by mass or more, 1% by mass or more, 1.5% by mass or more, 2% by mass or more, 2.5% by mass or more, 3% by mass or more, or 3.3% by mass or more. Alternatively, it can be 3.3% by mass or less, 3% by mass or less, 2.5% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, 0.9% by mass or less, 0.8% by mass or less, 0.6% by mass or less, 0.5% by mass or less, or 0.4% by mass or less.

[0066] When the resin component in the resin composition is set to 100% by mass, the content of component (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, 8% by mass or less, or 5% by mass or less.

[0067] It should be noted that, unless otherwise specified, the content of each component in the resin composition in this invention refers to the value when the non-volatile component in the resin composition is set to 100% by mass. The non-volatile component refers to the component other than the solvent described later in (H) of the components constituting the resin composition. Furthermore, the resin component of the resin composition refers to the component of the non-volatile component of the resin composition after removing the inorganic filler material.

[0068] <(B) Thermosetting Resins> The resin composition contains a thermosetting resin (B) as component (B). The thermosetting resin (B) as component (B) does not include those belonging to component (A). The type of thermosetting resin (B) is not particularly limited as long as it can be cured by heat. One type of thermosetting resin (B) may be used alone or in combination of two or more types.

[0069] (B) The thermosetting resin preferably has functional groups capable of inducing thermosetting. Examples of functional groups include, for instance, epoxy groups; free radical polymerizable unsaturated groups such as maleimide, vinyl, allyl, styrene, vinylphenyl, acryloyl, methacryloyl, fumaroyl, and maleyl; etc. As a functional group of the thermosetting resin (B), it is preferable to have any one of epoxy, maleimide, and styrene groups. Furthermore, it is preferable to have two or more functional groups in one molecule.

[0070] As the (B) thermosetting resin, for example, (B-1) epoxy resin, (B-2) curing agent, (B-3) free radical polymerizable resin, etc. can be used. As the (B) thermosetting resin, it is preferable to include any one of (B-1) epoxy resin, (B-2) curing agent and (B-3) free radical polymerizable resin, and more preferably to include (B-1) epoxy resin and (B-2) curing agent.

[0071] -(B-1) Epoxy Resin- (B-1) epoxy resin, as component (B), refers to a thermosetting resin having epoxy groups. (B-1) epoxy resin can be used alone or in combination with two or more types.

[0072] Examples of (B-1) epoxy resins include, for example, bixylenol-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, bisphenol AF-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenol-type epoxy resins, naphthol phenolic varnish-type epoxy resins, phenol phenolic varnish-type epoxy resins, tert-butylcatechol-type epoxy resins, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ester-type epoxy resins, and glycidyl... Cyclohexane-type epoxy resin, alkyl glycidyl ether-type epoxy resin, cresol phenolic varnish-type epoxy resin, biphenyl-type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane-type epoxy resin, cyclohexane-diethanol-type epoxy resin, naphthalene ether-type epoxy resin, tris(hydroxymethyl)-type epoxy resin, tetraphenylethane-type epoxy resin, phenol-benzopyrrolidone (FEN)-type epoxy resin, etc.

[0073] The resin composition preferably includes an epoxy resin having two or more epoxy groups per molecule as component (B-1). From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of epoxy resin having two or more epoxy groups per molecule relative to 100% by mass of (B-1) epoxy resin is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0074] (B-1) Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition, as component (B-1), may contain only liquid epoxy resin, only solid epoxy resin, or a combination of both. From the viewpoint of significantly obtaining the effects of the present invention, a combination of liquid epoxy resin and solid epoxy resin is preferred.

[0075] As a liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0076] As liquid epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenolic varnish type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanediol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin with butadiene structure, glycidyl cyclohexane type epoxy resin, phenol benzopyrrolidone type epoxy resin, alkyl glycidyl ether type epoxy resin are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin are more preferred.

[0077] Specific examples of liquid epoxy resins include: DIC's "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin); Mitsubishi Chemical's "828US", "jER828EL", "825", and "Epikote828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical's "jER807" and "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical's "jER152" (phenolic varnish type epoxy resin); Mitsubishi Chemical's "630" and "630LSD" (glycidylamine type epoxy resin); Nippon Steel Chemical & Materials Co., Ltd.'s "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); Nagase ChemteX's "EX-721" (glycidyl ester type epoxy resin); and Daicel's "Celloxide". 2021P (alicyclic epoxy resin with an ester backbone); Daicel's PB-3600 (an epoxy resin with a butadiene structure); Nippon Steel Chemical & Materials Co., Ltd.'s ZX1658 and ZX1658GS (liquid 1,4-glycidylcyclohexane type epoxy resin); Mitsubishi Chemical Co., Ltd.'s YED216D (alkyl glycidyl ether type epoxy resin), etc. These can be used individually or in combination of two or more.

[0078] As a solid epoxy resin, it is preferred to be a solid epoxy resin having two or more epoxy groups in one molecule, more preferably a solid epoxy resin having three or more epoxy groups in one molecule, and even more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule.

[0079] As a solid epoxy resin, the preferred types are xylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol-phenolic varnish-type epoxy resin, dicyclopentadiene-type epoxy resin, triphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthalene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with biphenyl-type epoxy resin being more preferred.

[0080] Specific examples of solid epoxy resins include: DIC's "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N-690" (cresol phenolic varnish type epoxy resin), "N-695" (cresol phenolic varnish type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", and "HP6000L" (naphthalene ether type epoxy resin); and Nippon Kayaku Co., Ltd.'s "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthalene phenolic varnish type epoxy resin), "NC3000H", and "NC30" (naphthalene etheric varnish type epoxy resin). "00", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthalene phenolic varnish type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bi-xylenol type epoxy resin), and "YX8800" (anthracite type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd. Epoxy resins include: "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; and "WHR-991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These resins can be used individually or in combination of two or more.

[0081] When liquid epoxy resin and solid epoxy resin are used in combination as component (B-1), their mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. By using the mass ratio of liquid epoxy resin to solid epoxy resin within this range, the desired effects of the present invention can be obtained.

[0082] The epoxy equivalent of component (B-1) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured body with sufficient crosslinking density can be provided. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be determined according to JIS K7236.

[0083] The weight-average molecular weight (Mw) of component (B-1) is preferably 100–5000, more preferably 150–3000, and even more preferably 200–1500. The weight-average molecular weight of the epoxy resin is the weight-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0084] When the non-volatile component is set to 100% by mass, the content of component (B-1) can be 0% by mass, preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0085] When the resin component in the resin composition is set to 100% by mass, the content of component (B-1) can be 0% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 25% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0086] - (B-2) Curing Agent - The curing agent (B-2), which is component (B), can react with the epoxy resin (B-1) to cure the resin composition. Examples of curing agents include: reactive ester resins, phenolic resins, carbodiimide resins, cyanate ester resins, acid anhydride resins, amine resins, benzoxazine resins, and thiol resins. Preferably, the curing agent (B-2) comprises both reactive ester resins and phenolic resins. One type of curing agent (B-2) can be used alone, or two or more can be used in combination.

[0087] As reactive ester resins, compounds having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are generally preferred. In addition to highly reactive ester groups, reactive ester resins may also contain allyl groups. When combined with epoxy resins, reactive ester resins can react with the epoxy resins to cure the resin composition; therefore, they are sometimes called "reactive ester-based curing agents." These reactive ester resins are preferably obtained through the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxyl compounds and / or thiols. Particularly from the viewpoint of significantly obtaining the effects of the present invention, reactive ester resins obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and more preferably reactive ester resins obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds. Examples of carboxylic acid compounds include, for instance, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, trihydroxybenzene, dicyclopentadiene-type diphenol compounds, and phenolic varnishes. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by the condensation of two phenol molecules with one dicyclopentadiene molecule.

[0088] Specifically, the preferred active ester resins are dicyclopentadiene-type active ester resins, naphthalene-type active ester resins containing a naphthalene structure, active ester resins containing acetylated phenolic varnishes, and active ester resins containing benzoylated phenolic varnishes. More preferably, they are selected from at least one of dicyclopentadiene-type and naphthalene-type active ester resins, and even more preferably, they are naphthalene-type active ester resins. As a dicyclopentadiene-type active ester resin, an active ester resin containing a dicyclopentadiene-type diphenol structure is preferred.

[0089] Commercially available reactive ester resins include, for example, reactive ester resins containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "EXB-8000H", and "EXB-8000L-65TM" (manufactured by DIC); and reactive ester resins containing a naphthalene structure such as "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", and "EXB-8100L-6...". Examples of reactive ester resins include "5T" and "EXB-8" (manufactured by DIC Corporation); examples of phosphorus-containing reactive ester resins include "EXB9401" (manufactured by DIC Corporation); examples of reactive ester resins containing acetylated phenolic varnishes include "DC808" (manufactured by Mitsubishi Chemical Corporation); examples of reactive ester resins containing benzoyl groups of phenolic varnishes include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "EXB-8500-65T" (manufactured by DIC Corporation); examples of reactive ester resins containing styrene and naphthalene structures include "PC1300-02-65T" and "PC1300-02-65MA" (manufactured by AIR WATER Corporation), etc.

[0090] The active ester equivalent of the active ester resin is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active ester equivalent indicates the mass of resin per 1 active ester group.

[0091] In one example, the range of weight-average molecular weight (Mw) of the reactive ester resin can be the same as that of the (B-1) epoxy resin.

[0092] When the non-volatile component in the resin composition is set to 100% by mass, the content of the active ester resin can be 0% by mass, preferably 1% or more by mass, more preferably 5% or more by mass, even more preferably 10% or more by mass, preferably 30% or less by mass, more preferably 25% or less by mass, even more preferably 20% or less by mass, or 15% or less by mass.

[0093] When the resin component in the resin composition is set to 100% by mass, the content of the active ester resin can be 0% by mass, preferably 1% or more by mass, more preferably 10% or more by mass, even more preferably 20% or more by mass, 30% or more by mass, preferably 70% or less by mass, more preferably 65% ​​or less by mass, and even more preferably 60% or less by mass.

[0094] The equivalent ratio of epoxy resin to reactive ester resin ([total count of reactive ester groups in the reactive ester resin] / [total count of epoxy groups in (B-1) epoxy resin]) is preferably 0.1 or more, more preferably 0.3 or more, further preferably 0.5 or more, 0.8 or more, or 1 or more, preferably 1.5 or less, more preferably 1.3 or less, and further preferably 1.1 or less. "Total count of epoxy groups in the epoxy resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. Furthermore, "Total count of reactive ester groups in the reactive ester resin" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the reactive ester resin present in the resin composition by the reactive ester group equivalent.

[0095] As a phenolic resin, a compound having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in one molecule can be used. When combined with an epoxy resin, the phenolic resin can react with the epoxy resin to cure the resin composition; therefore, it is sometimes called a "phenolic curing agent." From the viewpoint of significantly obtaining the effects of the present invention, the phenolic resin is preferably a phenolic resin having a phenolic varnish structure. Furthermore, from the viewpoint of adhesion, a nitrogen-containing phenolic resin is preferred, and a phenolic resin containing a triazine skeleton is more preferred. Among these, from the viewpoint of significantly obtaining the effects of the present invention, a phenolic varnish resin containing a triazine skeleton is preferred. Specific examples of phenolic resins include, for instance, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Corporation; “NHN”, “CBN”, “GPH” manufactured by Nippon Kayaku Co., Ltd.; “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375”, “SN-395” manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; and “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “TD-2090-60M”, “KA-1163” manufactured by DIC Corporation.

[0096] As a carbodiimide resin, a compound having one or more, preferably two or more, carbodiimide structures in one molecule and lacking free radical polymerizable groups can be used. When combined with epoxy resin, the carbodiimide resin can react with the epoxy resin to cure the resin composition, and is therefore sometimes called a "carbodiimide-based curing agent".

[0097] Specific examples of carbodiimide resins include: aliphatic carbodiimides such as tetramethylene-bis(tert-butylcarbodiimide) and cyclohexanebis(methylene-tert-butylcarbodiimide); aromatic carbodiimides such as phenylene-bis(xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); and poly(phenylenecarbodiimide). Aromatic polycarbodiimides such as poly(naphthylcarbodiimide), poly(tolylcarbodiimide), poly(methyldiisopropylphenylcarbodiimide), poly(triethylphenylcarbodiimide), poly(diethylphenylcarbodiimide), poly(triisopropylphenylcarbodiimide), poly(diisopropylphenylcarbodiimide), poly(xylenecarbodiimide), poly(tetramethylxylenecarbodiimide), poly(methylenediphenylcarbodiimide), and poly[methylenebis(methylphenyl)carbodiimide] are also included.

[0098] Commercially available carbodiimide resins include, for example, "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nisshinbo Chemical Co., Ltd.; and "Stabaxol P", "Stabaxol P100", "Stabaxol P400" and "Hycasyl510" manufactured by LANXESS Co., Ltd.

[0099] As cyanate ester resins, compounds having one or more, preferably two or more cyanate ester groups in one molecule can be used. When combined with epoxy resins, cyanate ester resins can react with epoxy resins to cure the resin composition, and are therefore sometimes called "cyanate ester-based curing agents". Examples of cyanate ester resins include, for instance, bisphenol A dicyanate, polyphenol cyanate, oligomeric (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide, and bis(4-cyanate phenyl) ether, etc., which are difunctional cyanate ester resins; polyfunctional cyanate ester resins derived from phenolic varnishes and cresol varnishes, etc.; and some triazine-modified prepolymers of these cyanate ester resins, etc. Specific examples of cyanate ester resins include "PT30" and "PT60" (both phenolic varnish-type multifunctional cyanate ester resins) manufactured by Arxada, "BA230" and "BA230S75" (prepolymers of bisphenol A dicyanate that have been partially or completely triazinized to become trimers), etc.

[0100] As an anhydride resin, compounds having one or more, preferably two or more, anhydride groups in one molecule can be used. When combined with epoxy groups, anhydride resins can react with epoxy resins to cure the resin composition; therefore, they are sometimes called "anhydride-based curing agents." Specific examples of anhydride resins include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and diphenyl Polymer anhydrides such as methyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl sulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(dehydrated trimellitate), and styrene-maleic acid resin copolymerized from styrene and maleic acid. Commercially available anhydride resins include, for example, "HNA-100", "MH-700", "MTA-15", "DDSA", and "OSA" manufactured by Shin Nippon Rika Co., Ltd.; "YH-306" and "YH-307" manufactured by Mitsubishi Chemical Co., Ltd.; "HN-2200" and "HN-5500" manufactured by RESONAC Co., Ltd.; and "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by Claybale Co., Ltd.

[0101] As amine resins, compounds having one or more, preferably two or more, amino groups in one molecule can be used. When combined with epoxy groups, amine resins can react with epoxy resins to cure the resin composition, and are therefore sometimes called "amine curing agents." Examples of amine resins include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, with aromatic amines being preferred. Amine resins are preferably primary or secondary amines, and more preferably primary amines. Specific examples of amine resins include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxybenzyl) 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. Commercially available amine resins include, for example, "SEIKACURE-S" manufactured by SEIKA Corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd.; "Epicure W" manufactured by Mitsubishi Chemical Co., Ltd.; and "DTDA" manufactured by Sumitomo Seika Co., Ltd.

[0102] Benzoxazine resins, when combined with epoxy resins, can react with the epoxy resins to cure the resin composition; therefore, they are sometimes called "benzoxazine curing agents." Specific examples of benzoxazine resins include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemicals; "HFB2006M" manufactured by Showa Polymers; and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0103] Thiol resins can react with epoxy resins when combined to cure the resin composition, and are therefore sometimes called "thiol-based curing agents". Examples of thiol resins include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetra(3-mercaptobutyrate), and tris(3-mercaptopropyl)isocyanurate.

[0104] (B-2) The active group equivalent of the curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The active group equivalent is the mass of the curing agent per 1 equivalent of active group.

[0105] (B-2) The weight-average molecular weight (Mw) of the curing agent is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight-average molecular weight of the resin can be determined by gel permeation chromatography (GPC) in the form of a polystyrene equivalent.

[0106] The equivalent ratio of (B-1) epoxy resin to (B-2) curing agent ([total count of active groups in (B-2) curing agent] / [total count of epoxy groups in (B-1) epoxy resin]) is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. "Total count of active groups in the curing agent" refers to the sum of all values ​​obtained by dividing the mass of the non-volatile components of the curing agent present in the resin composition by the equivalent amount of active groups.

[0107] When the non-volatile component in the resin composition is set to 100% by mass, the content of the (B-2) curing agent can be 0% by mass, preferably 1% or more by mass, more preferably 5% or more by mass, even more preferably 10% or more by mass, preferably 30% or less by mass, more preferably 25% or less by mass, and even more preferably 20% or less by mass.

[0108] When the resin component in the resin composition is set to 100% by mass, the content of the (B-2) curing agent can be 0% by mass, preferably 1% or more by mass, more preferably 40% or more by mass, further preferably 45% or more by mass, more preferably 50% or more by mass, preferably 70% or less by mass, more preferably 65% ​​or less by mass, and further preferably 60% or less by mass.

[0109] -(B-3) Free radical polymerizable resin- (B-3) free radical polymerizable resin, as component (B), refers to a resin having one or more (preferably two or more) free radical polymerizable unsaturated groups in one molecule. (B-3) free radical polymerizable resin can be used alone or in combination with two or more types.

[0110] Examples of free radical polymerizable unsaturated groups include one or more selected from maleimide, vinyl, allyl, styrene, vinylphenyl, acryloyl, methacryloyl, fumaroyl, and maleyl. Preferably, the free radical polymerizable unsaturated group includes any one of maleimide, vinyl, styrene, acryloyl, and methacryloyl, and more preferably, any one of maleimide and styrene. Therefore, from the viewpoint of significantly obtaining the effects of the present invention, the free radical polymerizable resin more preferably includes any one of maleimide resin, (meth)acrylic resin, and vinyl resin.

[0111] As a maleimide resin, there is no particular limitation on its type as long as it has one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl) in one molecule. Examples of maleimide resins include (1) "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", and "BMI-689" (all of which are Designer Molecules). (1) Maleimide resins containing an aliphatic skeleton (preferably an aliphatic skeleton with 36 carbon atoms from dimeric diamine), such as “SLK6895-T90” (Shin-Etsu Chemical Co., Ltd.) and “BMI-TMH” (Yamato Chemical Co., Ltd.); (2) Maleimide resins containing an indane skeleton as described in Patent Application Publication No. 2020-500211 of the Japan Invention Association; (3) Maleimide resins containing an aromatic ring skeleton that is directly bonded to the nitrogen atom of the maleimide group, such as “MIR-3000-70MT”, “MIR-5000-60T” (both manufactured by Nippon Kayaku Co., Ltd.), “BMI-4000”, “BMI-2300” (both manufactured by Yamato Chemical Co., Ltd.), “BMI-70”, and “BMI-80” (both manufactured by KI Chemical Co., Ltd.).

[0112] As a (meth)acrylic resin, its type is not particularly limited as long as it has one or more (preferably two or more) (meth)acryloyl groups in one molecule; it can be a monomer or an oligomer. Here, the term "(meth)acryloyl" is a general term for acryloyl and methacryloyl groups. In addition to (meth)acrylic ester monomers, other examples of (meth)acrylic resins include "A-DOG" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), "DCP-A" (manufactured by Kyoeisha Chemical Co., Ltd.), "SA9000" (manufactured by SABIC Corporation), "NPDGA", "FM-400", "R-604", "R-684", "THE-330", "PET-30", "DPHA", and "DPCA" (all manufactured by Nippon Kayaku Co., Ltd.).

[0113] It should be noted that component (B-3) may or may not contain a urea-containing (meth)acrylamide compound as shown in the following formula as a (meth)acrylic resin. That is, the urea-containing (meth)acrylamide compound shown in the following formula can be removed from component (B-3).

[0114] [Chemistry 7] Vinyl resins are not particularly limited in type as long as they have one or more (preferably two or more) vinyl groups in one molecule. For example, vinyl resins containing a styrene group are sometimes also called styrene resins, where the styrene group has one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of vinyl resins include, for instance, low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl) ether; high molecular weight (molecular weight 1000 or more) styrene resins such as vinylbenzyl modified polyphenylene ether resins and styrene-divinylbenzene copolymers; and styrene compounds having either a phenylpyrimidine backbone or a 1,1-diphenylcyclohexane backbone. Commercially available vinyl and styrene resins include, for example, “ODV-XET(X03)”, “ODV-XET(X04)”, and “ODV-XET(X05)” (styrene-divinylbenzene copolymer) manufactured by Nippon Steel Chemicals & Materials Co., Ltd., and “OPE-2St 1200” and “OPE-2St 2200” (vinyl benzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.

[0115] When the non-volatile component in the resin composition is set to 100% by mass, the content of (B-3) free radical polymerizable resin can be 0% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less.

[0116] When the resin component in the resin composition is set to 100% by mass, the content of (B-3) free radical polymerizable resin can be 0% by mass, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 1% by mass or more, 5% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, or 1% by mass or less.

[0117] When the non-volatile component in the resin composition is set to 100% by mass, the content of the thermosetting resin (B) (the total content of components (B-1), (B-2) and (B-3)) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, or 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, and further preferably 30% by mass or less.

[0118] When the resin component in the resin composition is set to 100% by mass, (B) the content of thermosetting resin is preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 94% by mass or less.

[0119] The mass ratio of component (B) to component (A) in the resin composition (component (B) / component (A)) is preferably 5 or more, more preferably 6 or more, further preferably 9 or more, greater than 9, 10 or more, 12 or more, 15 or more, or 16 or more, preferably 300 or less, more preferably 250 or less, further preferably 200 or less, 150 or less, 100 or less, 80 or less, 60 or less, 50 or less, 40 or less, or 30 or less.

[0120] In another embodiment, the mass ratio of component (B) to component (A) in the resin composition (component (B) / component (A)) can be 20 or more, 23 or more, 25 or more, 26 or more, 27 or more, or 28 or more. Alternatively, it can be 28 or less, 27 or less, 26 or less, 25 or less, 23 or less, 20 or less, or 16 or less.

[0121] <(C) Inorganic filler materials> As an optional component, the resin composition may contain (C) inorganic filler as component (C). By containing (C) inorganic filler in the resin composition, a cured product with low dielectric properties and a low coefficient of linear thermal expansion can be obtained. (C) inorganic filler is usually contained in the resin composition in the form of particles. Component (C) may be used alone or in combination of two or more.

[0122] Inorganic compounds are used as the inorganic filler material in (C). Examples of inorganic filler materials in (C) include, for example, silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Furthermore, spherical silica is preferred as silica.

[0123] Commercially available products as (C) inorganic filler materials include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemicals & Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; and "CELLSPHERES MGH-005" manufactured by Pacific Cement Co., Ltd.

[0124] (C) The average particle size of the inorganic filler material is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably greater than 0.1 μm, 0.2 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less.

[0125] (C) The average particle size of inorganic filler materials can be determined using laser diffraction and scattering based on the Mie scattering theory. Specifically, a laser diffraction and scattering particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler material based on volume, and the median diameter can be set as the average particle size for measurement. The sample to be measured can be a sample obtained by weighing 100 mg of inorganic filler material and 10 g of methyl ethyl ketone into a small bottle and dispersing it ultrasonically for 10 minutes. Using a laser diffraction and scattering particle size distribution measuring device, the particle size distribution of the inorganic filler material based on volume is measured in a flow cell mode with the light source wavelength set to blue and red. The average particle size, which is the median diameter, can be calculated from the obtained particle size distribution. Examples of laser diffraction and scattering particle size distribution measuring devices include, for example, the "LA-960" manufactured by Horiba Manufacturing Co., Ltd.

[0126] (C) The preferred BET specific surface area of ​​the inorganic filler material is 0.1 m². 2 / g or more, more preferably 0.5m 2 / g or more, further preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 / g or less.

[0127] (C) The specific surface area of ​​inorganic filler materials can be determined by the BET method using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH), which adsorbs nitrogen onto the sample surface and calculates the specific surface area using the BET multi-point method.

[0128] From the viewpoint of improving moisture resistance and dispersibility, (C) inorganic filler materials are preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorinated silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. A single surface treatment agent can be used, or two or more can be used in any combination.

[0129] Commercially available surface treatment agents include, for example, "KBM403" (3-epoxypropoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM-4803" (long-chain epoxy silane coupling agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0130] From the viewpoint of improving the dispersibility of inorganic filler materials, the degree of surface treatment using the surface treatment agent is preferably controlled within a specific range. Specifically, 100% by mass of the inorganic filler material is preferably surface treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass, and even more preferably with 0.3% to 2% by mass.

[0131] The degree of surface treatment using surface treatment agents can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m³. 2 The above, and more preferably, is 0.1 mg / m³ 2 The above, and more preferably, is 0.2 mg / m³ 2 That's all. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition, 1.0 mg / m³ is preferred. 2 The following, more preferably, is 0.8 mg / m 2 The following, and more preferably, is 0.5 mg / m². 2 the following.

[0132] (C) The carbon content per unit surface area of ​​the inorganic filler material can be determined after washing the surface-treated inorganic filler material with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the surface-treated inorganic filler material, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid components, the carbon content per unit surface area of ​​the inorganic filler material can be determined using a carbon analyzer. A carbon analyzer such as the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0133] Furthermore, the degree of surface treatment using the surface treatment agent can be evaluated by the carbon content per unit mass of the inorganic filler material. The carbon content per unit mass of the inorganic filler material is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, it is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. (C) The carbon content per unit mass of the inorganic filler material can be determined using a carbon analyzer in the same manner as the carbon content per unit surface area of ​​(C) the inorganic filler material.

[0134] When the non-volatile component in the resin composition is set to 100% by mass, the content of (C) inorganic filler material is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 60% by mass or more, or 65% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, or 75% by mass or less.

[0135] <(D) Thermoplastic Resins> The resin composition may also contain (D) thermoplastic resin as component (D) as any component. The (D) thermoplastic resin as component (D) does not include those belonging to components (A) to (C) above. Component (D) may be used alone or in combination of two or more.

[0136] Examples of (D) thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamide-imide resin, polyether-imide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc.

[0137] (D) The weight-average molecular weight of the thermoplastic resin converted to polystyrene is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably 18,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less. (D) The weight-average molecular weight of the thermoplastic resin converted to polystyrene is determined by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight of (D) the thermoplastic resin converted to polystyrene can be determined using an LC-9A / RID-6A manufactured by Shimadzu Corporation, a Shodex K-800P / K-804L / K-804L manufactured by Showa Denko Corporation, and a mobile phase such as chloroform, at a column temperature of 40°C, and calculated using a standard curve of standard polystyrene.

[0138] Examples of phenoxy resins include those having one or more skeletons selected from the following: bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic varnish skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal end of the phenoxy resin may have any functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins can be used alone or in combination of two or more. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both containing a bisphenol A backbone), "YX8100" (containing a bisphenol S backbone), "YX7800BH40" (containing a fluorene backbone), and "YX6954" (containing a bisphenol acetophenone backbone). Other examples include Nippon Steel Chemicals & Materials' "FX280" and "FX293," and Mitsubishi Chemical's "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," and "YL7482," etc.

[0139] Examples of polyvinyl acetal resins include, for example, polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include, for example, the S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemicals Co., Ltd.

[0140] Specific examples of polyimide resins include "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Rikka Co., Ltd. Other specific examples of polyimide resins include linear polyimides (the polyimide described in Japanese Patent Application Publication No. 2006-37083) obtained by reacting difunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic anhydride, and modified polyimides such as polyimides containing a polysiloxane backbone (the polyimides described in Japanese Patent Application Publication Nos. 2002-12667 and 2000-319386, etc.).

[0141] The resin composition of the present invention may or may not contain polyimide resin other than component (A) above. That is, polyimide resin other than component (A) above can be excluded from the resin composition of the present invention.

[0142] Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Other examples of polyamide-imide resins include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane backbone) manufactured by Resonac Co., Ltd.

[0143] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyphenylene ether resins include "OPE-2St 1200" oligomeric phenylene ether-styrene resin manufactured by Mitsubishi Gas Chemical Co., Ltd. Specific examples of polyetheretherketone resins include "SUMIPLOY K" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of polyetherimide resins include "ULTEM" manufactured by GE.

[0144] Specific examples of polysulfone resins include polysulfones such as "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0145] Examples of polyolefin resins include low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, and other ethylene-based copolymers; and polyolefin elastomers such as polypropylene and ethylene-propylene block copolymers.

[0146] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexanedimethyl terephthalate resin.

[0147] As the (D) thermoplastic resin, phenoxy resin is preferred. Among them, as the (D) thermoplastic resin, phenoxy resin with a weight-average molecular weight of 40,000 or more is preferred.

[0148] When the non-volatile component in the resin composition is set to 100% by mass, the content of (D) thermoplastic resin can be 0% by mass, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 1.5% by mass or less, and even more preferably 1% by mass or less.

[0149] When the resin component in the resin composition is set to 100% by mass, the content of (D) thermoplastic resin is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less.

[0150] <(E) Organic filler materials> As an optional component, the resin composition may also contain organic filler material (E) as component (E). This organic filler material (E) does not include those belonging to components (A) to (D) above. The organic filler material (E) is generally immiscible with resin components other than the organic filler material (E) and is contained in the resin composition in a particulate state, and is contained in the cured product to maintain this particulate state. Furthermore, one type of organic filler material (E) may be used alone, or two or more may be used in combination.

[0151] As the (E) organic filler material, particles of organic material can be used. The organic material contained in the (E) organic filler material is preferably a rubber component. Examples of rubber components include, for example, silicone-based elastomers such as polydimethylsiloxane; olefin-based thermoplastic elastomers such as polybutadiene, polyisoprene, polychloroprene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, and ethylene-propylene-butene terpolymer; and acrylic-based thermoplastic elastomers such as poly(meth)acrylate, poly(meth)acrylate, poly(cyclohexyl methacrylate), and poly(octyl methacrylate). Furthermore, silicone-based rubbers such as polysiloxane rubber can also be mixed into the rubber component. The glass transition temperature of the rubber component contained in the rubber particles is, for example, below 0°C, preferably below -10°C, more preferably below -20°C, and even more preferably below -30°C.

[0152] (E) The organic filler material can be a core-shell type rubber particle formed by a core particle and a shell, wherein the core particle contains the rubber components listed above, and the shell is formed by graft copolymerization of monomer components capable of copolymerizing with the rubber components contained in the core particle. Here, core-shell type does not necessarily refer only to those core particles and shells that can be clearly distinguished, but also includes those where the boundary between the core particle and the shell is unclear, and the core particle may not be completely covered by the shell.

[0153] Specific examples of (G) organic filler materials include, for example, Samsung SDI's "CHT"; Techno UMG's "B602"; DOW's "PARALOID EXL-2602", "PARALOID EXL-2603", "PARALOID EXL-2655", "PARALOID EXL-2311", "PARALOID EXL-2313", "PARALOID EXL-2315", "PARALOID KM-330", "PARALOID KM-336P", "PARALOID KCZ-201"; Mitsubishi Rayon's "METABLEN C-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200"; and KANEKA's "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-600", "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200"; and KANEKA's "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-600", "Kane Ace M-223A", "METABLEN E-901", "METABLEN S-2001", "METABLEN W-450A", "METABLEN SRK-200". "AceM-400", "Kane Ace M-580", "Kane Ace MR-01", "STAFYROID AC3355", "STAFYROID AC3816", "STAFYROID AC3816N", "STAFYROID AC3832", "STAFYROID AC4030", "STAFYROID AC3364" manufactured by AICA Industries, etc.

[0154] When the non-volatile component in the resin composition is set to 100% by mass, the content of (E) organic filler material is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0155] When the resin component in the resin composition is set to 100% by mass, the content of the organic filler material (E) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8.5% by mass or less.

[0156] <(F) Curing Accelerator> The resin composition may also contain (F) a curing accelerator as an optional component. The (E) curing accelerator, which is component (F), does not include those belonging to components (A) to (E) above. The (F) curing accelerator can act as a catalyst on the reaction of the (B-1) epoxy resin to promote the curing of the resin composition.

[0157] Examples of (F) curing accelerators include: phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. A single (F) curing accelerator can be used alone, or in combination of two or more.

[0158] Examples of phosphorus-based curing accelerators include: tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutyldecanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitictetrate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butyldimethylphosphonium tetraphenylborate, and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, and p-tolyltriphenylphosphonium tetrap-toluene. Aromatic phosphonium salts such as triphenylphosphonium tetraphenylborane, tetraphenylphosphonium tetrap-tolylborane, triphenylethylphosphonium tetraphenylborane, tri(3-methylphenyl)ethylphosphonium tetraphenylborane, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborane, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphonium-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphonium-benzoquinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, and di-tert-butyl(2-butenyl)phosphine. Aliphatic phosphines such as triphenylphosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, and tricyclohexylphosphine; tributylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine, etc. Aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0159] Examples of urea-based curing accelerators include: 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. Aromatic dimethylureas include 1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea)[toluenebisdimethylurea], etc.

[0160] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0161] Examples of imidazole-based curing accelerators include, for example, 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 2,4-diamino-6-[2'-methylimidazolium-(1')] [Ethyl-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and adducts of imidazole compounds with epoxy resins. Commercially available imidazole-based curing accelerators include, for example, "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK", "2MA-OK-PW", "2PHZ", "2PHZ-PW", "Cl1Z", "Cl1Z-CN", "Cl1Z-CNS", and "C11Z-A" manufactured by Shikoku Chemical Co., Ltd.; and "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.

[0162] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) and cobalt(III) acetylacetone, organocopper complexes such as copper(II) acetylacetone, organozinc complexes such as zinc(II) acetylacetone, organoiron complexes such as iron(III) acetylacetone, organonickel complexes such as nickel(II) acetylacetone, and organomanganese complexes such as manganese(II) acetylacetone. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0163] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene. Commercially available amine-based curing accelerators can be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno.

[0164] The content of (F) curing accelerator relative to 100% by mass of the non-volatile components in the resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0165] Relative to 100% by mass of the resin component in the resin composition, the content of (F) curing accelerator is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 6% by mass or less, and even more preferably 3% by mass or less.

[0166] <(G) Any additives> The resin composition may further include any additives in (G) as any component. Any additives in (G) as component (G) do not include those belonging to components (A) to (F) above. Examples of any additives in (G) include organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium dioxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentonite and montmorillonite; defoamers such as silicone-based defoamers, acrylic defoamers, fluorinated defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion enhancers such as ureasilanes; adhesion enhancers such as triazole-based, tetraazole-based, and triazine-based adhesion enhancers; hindered phenols. Antioxidants such as stilbene derivatives; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorinated surfactants and organosilicon surfactants; flame retardants such as phosphorus-based (e.g., phosphate compounds, phosphazene compounds, phosphonic acid compounds, red phosphorus), nitrogen-based (e.g., melamine sulfate), halogen-based, and inorganic (e.g., antimony trioxide); dispersants such as phosphate ester-based, polyoxyethylene-based, acetylene-based, organosilicon-based, anionic, and cationic dispersants; stabilizers such as borate-based, titanate-based, aluminate-based, zirconate-based, isocyanate-based, carboxylic acid-based, and carboxylic anhydride-based stabilizers. (G) Any additive may be used alone or in combination of two or more.

[0167] The resin composition of the present invention may also contain or exclude methylphenyl silicone resin as component (G). That is, the inclusion of methylphenyl silicone resin can be excluded from the resin composition of the present invention. It should be noted that methylphenyl silicone resin refers to a silicone resin having both methyl and phenyl groups.

[0168] The resin composition of the present invention may or may not contain a copolymer containing an unsaturated monomer of styrene and maleic anhydride as component (G). That is, copolymers containing an unsaturated monomer of styrene and maleic anhydride can be excluded from the resin composition of the present invention.

[0169] <(H) solvent> The resin composition may further comprise, in combination with non-volatile components such as components (A) to (G) above, a solvent (H) as an optional volatile component. Organic solvents are typically used as the solvent (H). Examples of organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; and 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and ethyl diglycol acetate. Ether ester solvents such as acetate, γ-butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) Solvents can be used alone or in combination of two or more.

[0170] The amount of solvent (H) relative to 100% by mass of all components in the resin composition can be, for example, less than 60% by mass, less than 40% by mass, less than 30% by mass, less than 20% by mass, less than 15% by mass, or less than 10% by mass.

[0171] <Method for manufacturing resin composition> A resin composition can be manufactured, for example, by mixing the components that a resin composition may contain. These components can be mixed partially or entirely simultaneously, or sequentially. During the mixing of the components, a suitable temperature can be set, allowing for temporary or continuous heating and / or cooling. Furthermore, stirring or agitation can be performed during the mixing of the components.

[0172] <Properties and Uses of Resin Compositions> The resin composition contains component (A), thus yielding cured products with excellent dielectric properties, elongation, and adhesion before and after HAST testing. Furthermore, cured products with high glass transition temperatures and low coefficients of linear thermal expansion (CTE) can also be obtained.

[0173] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes exhibits a low dielectric constant. Therefore, the aforementioned cured product provides an insulating layer with a low dielectric constant. The dielectric constant is preferably 4 or less, more preferably 3.5 or less, and even more preferably 3.4 or less. There is no particular limitation on the lower limit; it can be set to 0.001 or more, etc. The dielectric constant can be determined according to the method described in the examples below.

[0174] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes exhibits a low dielectric loss tangent. Therefore, the aforementioned cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.003 or less, more preferably 0.0029 or less, and even more preferably 0.0026 or less. There is no particular limitation on the lower limit; it can be set to 0.00001 or more, etc. The dielectric loss tangent can be measured according to the method described in the examples below.

[0175] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes exhibits high elongation. Therefore, the aforementioned cured product provides an insulating layer with high elongation, thereby suppressing crack formation. The elongation is preferably 0.8% or more, more preferably 1% or more, further preferably 1.5% or more, or 2% or more. There is no particular upper limit, and it can be set to 10% or less, etc. The elongation can be measured according to the method described in the examples below.

[0176] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes exhibits excellent adhesion to the copper foil before the Accelerated Environmental Testing (HAST) test. Therefore, the aforementioned cured product provides an insulating layer with excellent adhesion (peel strength) to the copper foil before the HAST test. The peel strength is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and even more preferably 0.6 kgf / cm or more. The upper limit of the peel strength can be set to 10 kgf / cm or less, etc. The peel strength can be measured according to the method described in the examples below.

[0177] The cured product obtained by heat curing the resin composition at 190°C for 90 minutes exhibits excellent adhesion to copper foil after accelerated environmental testing (HAST). Therefore, the aforementioned cured product provides an insulating layer with excellent adhesion (peel strength) to copper foil after HAST testing. The peel strength after HAST testing is preferably 0.2 kgf / cm or more, more preferably 0.3 kgf / cm or more, and even more preferably 0.35 kgf / cm or more. The upper limit of the peel strength after HAST testing can be set to 10 kgf / cm or less, etc. The peel strength can be measured according to the method described in the examples below.

[0178] Cured products obtained by heat curing the resin composition at 190°C for 90 minutes typically exhibit a high glass transition temperature (Tg). Therefore, the aforementioned cured products provide an insulating layer with a high glass transition temperature. The glass transition temperature is preferably 135°C or higher, more preferably 140°C or higher, and even more preferably 145°C or higher. There is no particular upper limit, and it can be set to 500°C or lower, etc. The glass transition temperature can be determined according to the method described in the examples below.

[0179] Cured products obtained by heat curing the resin composition at 190°C for 90 minutes typically exhibit a low coefficient of linear thermal expansion (CTE). Therefore, the aforementioned cured product provides an insulating layer with a low CTE. The CTE is preferably 25 ppm / °C or less, more preferably 23 ppm / °C or less, and even more preferably 22 ppm / °C or less. The lower limit is not particularly limited and can be set to 1 ppm / °C or more, etc. The CTE can be determined according to the method described in the examples described later.

[0180] The resin compositions of the present invention can yield cured products with excellent dielectric properties, elongation, and adhesion before and after HAST testing. Furthermore, cured products with high glass transition temperatures and low coefficients of linear thermal expansion (CTE) are also generally obtained. Therefore, the resin compositions of the present invention can be suitably used as resin compositions for insulating applications. Specifically, they can be suitably used as resin compositions for forming insulating layers (resin compositions for forming insulating layers for conductor layers), which are used to form conductor layers (including rewiring layers) formed on the insulating layer.

[0181] Furthermore, in circuit boards such as printed wiring boards described later, resin compositions suitable for forming insulating layers of circuit boards (resin compositions for forming insulating layers of multilayer printed wiring boards) and resin compositions for forming interlayer insulating layers of printed wiring boards (resin compositions for forming interlayer insulating layers of printed wiring boards) can be used appropriately.

[0182] Furthermore, for example, when manufacturing a semiconductor chip package via steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for forming a rewiring layer (resin composition for forming a rewiring layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). During the manufacturing of the semiconductor chip package, a rewiring layer may also be further formed on the sealing layer.

[0183] (1) The step of laminating a temporary fixing film on the substrate, (2) The step of temporarily fixing the semiconductor chip onto the temporary fixing film. (3) The step of forming a sealing layer on a semiconductor chip, (4) The step of peeling the substrate and temporary fixing film from the semiconductor chip. (5) The step of forming a rewiring layer as an insulating layer on the surface of a semiconductor chip where the substrate and temporary fixing film have been stripped, and (6) The step of forming a redistribution layer as a conductor layer on the redistribution layer.

[0184] [Resin Sheets] The resin sheet of the present invention comprises a support and a resin composition layer formed of the resin composition of the present invention disposed on the support. The resin composition layer comprises the above-described resin composition, preferably only the above-described resin composition.

[0185] From the viewpoint of thinness, the thickness of the resin composition layer in the resin sheet is preferably 200 μm or less, more preferably 150 μm or less, and even more preferably 100 μm or less. The lower limit of the thickness of the resin composition layer can be, for example, 1 μm or more, 3 μm or more, 5 μm or more, etc.

[0186] Examples of supports include plastic film, metal foil, and release paper, with plastic film and metal foil being preferred.

[0187] When a plastic film is used as a support, examples of plastic materials include, for example, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), acrylics such as polycarbonate (hereinafter sometimes abbreviated as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0188] When using metal foil as a support, examples of metal foil include copper foil and aluminum foil, with copper foil being preferred. As copper foil, foil containing a single metal such as copper can be used, or foil containing an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

[0189] It should be noted that metal foil such as copper foil may or may not be used as the support. That is, the method of using metal foil such as copper foil as the support can be excluded from the resin sheet of the present invention.

[0190] Surface treatments such as matte finish, corona treatment, and antistatic treatment can be applied to the surface of the support that is bonded to the resin composition layer.

[0191] As a support, a support with a release layer can be used on the surface that bonds to the resin composition layer. Examples of release agents used in the release layer of the support with a release layer include, for example, one or more release agents selected from alkyd-based, polyolefin-based, polyurethane-based, and silicone-based release agents. Commercially available products can be used as the support with a release layer, such as PET films having a release layer primarily composed of silicone-based or alkyd resin-based release agents, i.e., LINTEC's "PET501010", "SK-1", "AL-5", and "AL-7"; Toray's "Lumirror T60"; Teijin's "Purex"; and UNITIKA's "Unipeel".

[0192] The thickness of the support is not particularly limited, but is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 75 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less. When using a support with a release layer, the overall thickness of the support with the release layer is preferably within the above range.

[0193] Resin sheets can have any components as needed. For example, resin sheets can have a protective film that protects the resin composition layer. The protective film is usually provided on the surface that is not bonded to the support of the resin composition layer (i.e., the surface opposite to the support). The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. When a protective film is provided, it can inhibit the adhesion and damage of dust on the surface of the resin composition layer.

[0194] Resin sheets can be manufactured, for example, by a method comprising forming a resin composition layer on a support. Specifically, a liquid (varnish-like) resin composition can be used directly, or a liquid (varnish-like) resin composition can be prepared by mixing a solvent with the resin composition, which is then applied to a support and dried as needed to form a thermoplastic resin composition layer, thereby manufacturing a resin sheet. The solvents used can be the same as those described as components of the resin composition in (I).

[0195] The resin composition can be coated using a coating apparatus such as a die coater. Drying can be performed by methods such as heating or blowing hot air. Drying conditions are not particularly limited, but drying is typically carried out with the solvent content in the resin composition layer typically reaching 10% by mass or less, preferably 5% by mass or less. The drying time may vary depending on the boiling point of the solvent; for example, when using a resin composition containing 30% to 60% by mass of solvent, a resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0196] The manufactured resin sheets can be rolled into rollers for storage. When the resin sheets have a protective film, they can usually be used by peeling off the protective film.

[0197] Resin sheets may not be used immediately after manufacturing. In such cases, the resin sheets are preferably stored in a frozen and / or refrigerated state after manufacturing in a manner that does not impair their properties. Storage in a frozen state is more preferable than storage in a frozen state. For example, the temperature conditions for storing the resin sheets in a frozen or refrigerated state are preferably 8°C or below, more preferably 0°C or below, and even more preferably -18°C or below. There is no particular limitation on the lower limit of this temperature; for example, it can be set to -40°C or above. When storing the resin sheets in a frozen or refrigerated state, it is preferable to thaw and adjust the temperature by placing the resin sheets in a usage environment (temperature 15–28°C, relative humidity 40–60% RH), and use them after the resin composition layer contained in the resin sheets reaches the same temperature as the usage environment, but this is not a limitation.

[0198] [Circuit board] One embodiment of the circuit board of the present invention includes an insulating layer formed from a cured product of the above-described resin composition. The insulating layer may consist solely of the cured product of the resin composition. The thickness of the insulating layer is not particularly limited; for example, it may be within the same range as the thickness of the resin composition layer on the resin sheet. Furthermore, the insulating layer may generally have the same properties as the cured product of the above-described resin composition.

[0199] Preferably, the circuit board includes an inner substrate on which the aforementioned insulating layer is provided. Furthermore, the circuit board may also include a conductor layer. For example, a conductor layer may also be provided on the insulating layer. Hereinafter, examples of preferred methods for manufacturing the circuit board will be described.

[0200] The preferred embodiment of the circuit board manufacturing method includes: The process of forming a resin composition layer on the inner substrate (I), and Step (II) for curing the resin composition layer.

[0201] "Inner layer substrate" refers to a component that serves as the substrate of a circuit board, such as glass epoxy resin substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. Furthermore, the inner layer substrate may have conductive layers on one or both sides. The conductive layers of the inner layer substrate may also be patterned. An inner layer substrate with conductive layers (circuit) formed on one or both sides of the substrate is sometimes called an "inner circuit board." In addition, intermediate components used to further form insulating layers and / or conductive layers during the manufacture of the circuit board are also included in the term "inner layer substrate." Furthermore, inner layer substrates with built-in components can also be used.

[0202] The formation of the resin composition layer on the inner layer substrate can be carried out, for example, by a formation method that includes coating the resin composition on the inner layer substrate and drying it as needed, preferably using a resin sheet. The method of forming the resin composition layer using a resin sheet typically involves laminating the resin sheet and the inner layer substrate. The lamination of the resin sheet and the inner layer substrate is performed in such a way that the resin composition layer of the resin sheet is bonded to the inner layer substrate. This lamination can be performed, for example, by heating and pressing the resin sheet onto the inner layer substrate from the support side. Examples of components for heating and pressing the resin sheet onto the inner layer substrate (hereinafter also referred to as "heat-pressing component") include, for example, heated metal plates (SUS end plates, etc.) or metal rollers (SUS rollers, etc.). It should be noted that the heat-pressing component is not pressed directly onto the resin sheet, but rather it is preferably pressed using an elastic material such as heat-resistant rubber so that the resin sheet fully follows the surface irregularities of the inner layer substrate.

[0203] The lamination of the inner substrate and the resin sheet can be performed using a vacuum lamination method. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C; the heating and pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably 0.29 MPa to 1.47 MPa; and the heating and pressing time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 26.7 hPa or less.

[0204] Lamination can also be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include the vacuum pressure laminator manufactured by Meiki Seisakusho, the vacuum dressing device manufactured by Nikko-Materials, and the intermittent vacuum pressure laminator.

[0205] A method for manufacturing a circuit board may include: after lamination, smoothing the resin sheet by applying pressure to a heat-pressing member under normal pressure (atmospheric pressure), for example, from the support side. The pressure conditions for the smoothing process can be set to the same conditions as the heat-pressing conditions for the lamination described above. The smoothing process can be performed using a commercially available laminating machine. Lamination and smoothing processes can be performed continuously using the aforementioned commercially available vacuum laminating machine.

[0206] The method for manufacturing the circuit board in this example includes a step (II) after step (I) in which a resin composition layer is cured. In step (II), by curing the resin composition layer, an insulating layer containing the cured resin composition can be formed.

[0207] The curing of the resin composition layer is usually carried out by heat curing. The heat curing conditions of the resin composition layer can vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C to 210°C. In addition, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0208] The method for manufacturing a circuit board may further include preheating the resin composition layer at a temperature lower than the curing temperature before thermal curing. For example, before thermal curing the resin composition layer, it is typically preheated at a temperature of 50°C to 150°C, preferably 60°C to 140°C, more preferably 70°C to 130°C for at least 5 minutes, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and even more preferably 15 minutes to 100 minutes. Preheating is usually performed after step (I). Furthermore, when a smoothing treatment is performed after the inner layer substrate and the resin sheet are laminated, preheating can usually be performed after the smoothing treatment.

[0209] When using resin sheets, the method for manufacturing a circuit board may include a step of peeling off a support from the resin sheet after the inner substrate and the resin sheet are laminated. The peeling off of the support may be performed between steps (I) and (II), or after step (II). Furthermore, when the method for manufacturing a circuit board, as described below, includes steps (III) of forming holes in an insulating layer, (IV) of roughening the insulating layer, and (V) of forming a conductor layer, the peeling off of the support may be performed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V).

[0210] The circuit board manufacturing method may further include a step (III) after step (II) of forming holes such as vias and through holes in the insulating layer. The method for forming the holes can be selected based on factors such as the composition of the resin composition used in forming the insulating layer. For example, drilling, laser processing, and plasma processing can be used to form the holes, with laser processing being preferred. For instance, holes can be formed by irradiating the insulating layer with a laser after the support has been peeled off, or by irradiating the insulating layer with a laser through the support. The size and shape of the holes can be appropriately determined based on the design of the circuit board.

[0211] The method for manufacturing a circuit board may also include a step (IV) of roughening the insulating layer. This roughening process roughens the surface of the insulating layer. Furthermore, it removes contaminants (resin residue) from the insulating layer. Therefore, this roughening process is sometimes referred to as a "contaminant removal process." For example, if a hole is formed in step (III), contaminants may form within the hole; therefore, it is preferable to perform the roughening process (IV) after step (III) to remove these contaminants.

[0212] There are no particular limitations on the steps and conditions of the roughening treatment; known steps and conditions commonly used in forming the insulating layer of a circuit board can be adopted. For example, the insulating layer can be roughened by sequentially performing a swelling treatment using a swelling solution, an oxidation treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution.

[0213] Examples of swelling solutions used in the roughening process include alkaline solutions and surfactant solutions, with alkaline solutions being preferred. Sodium hydroxide solution and potassium hydroxide solution are more preferred. Commercially available swelling solutions include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN. Swelling treatment using a swelling solution can be performed, for example, by immersing the insulating layer in a swelling solution at 30°C to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to a suitable level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 to 15 minutes.

[0214] Examples of oxidizing agents used in roughening processes include alkaline permanganate solutions obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. Oxidation treatment using alkaline permanganate solutions or similar oxidizing agents is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60°C to 100°C for 10 to 30 minutes. Furthermore, the concentration of permanganate in the alkaline permanganate solution is preferably 5% to 10% by mass. Commercially available oxidizing agents include, for example, alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by ATOTECH JAPAN.

[0215] The neutralizing solution used in the roughening process is preferably an acidic aqueous solution, and commercially available examples include, for instance, "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN. The neutralization process using the neutralizing solution can be performed by immersing the surface that has undergone oxidation treatment with an oxidizing agent in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes. From an operational point of view, it is preferable to immerse the object that has undergone oxidation treatment with an oxidizing agent in a neutralizing solution at 40°C to 70°C for 5 to 20 minutes.

[0216] The method of manufacturing a circuit board may also include a step (V) of forming a conductor layer on an insulating layer. When the method of manufacturing a circuit board includes step (III) or (IV), the step (V) of forming a conductor layer is generally preferably performed after steps (III) and (IV).

[0217] The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer can be a single metal layer or an alloy layer. Examples of alloy layers include layers formed from alloys of two or more metals selected above (e.g., nickel-chromium alloys, copper-nickel alloys, and copper-titanium alloys). From the viewpoints of versatility, cost, and ease of patterning in conductor layer formation, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloys, copper-nickel alloys, or copper-titanium alloys, are preferred. More preferably, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloys, are even more preferred. A single metal layer of copper is also preferred.

[0218] The conductor layer can have a single-layer structure or a multi-layer structure comprising two or more single-metal layers or alloy layers made of different types of metals or alloys. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single-metal layer of chromium, zinc, or titanium, or an alloy layer of nickel-chromium alloy.

[0219] The thickness of the conductor layer depends on the desired circuit board design, and is preferably 3μm to 35μm, more preferably 5μm to 30μm.

[0220] The conductor layer can be formed by plating. For example, a conductor layer with the desired wiring pattern can be formed by plating the surface of the insulating layer using conventionally known techniques such as semi-additive and fully additive methods. From the viewpoint of ease of manufacturing, the semi-additive method is preferred. An example of forming a conductor layer by the semi-additive method is shown below.

[0221] First, an electroless plating layer (plating seed layer) is formed on the surface of the insulating layer through electroless plating. Next, a mask pattern is formed on the formed electroless plating layer, exposing a portion of the electroless plating layer corresponding to the desired wiring pattern. After forming an electrolytic plating layer on the exposed electroless plating layer through electrolytic plating, the mask pattern is removed. Then, the unwanted electroless plating layer is removed by etching, thereby forming a conductor layer with the desired wiring pattern.

[0222] As another example, the conductor layer can be formed using metal foil. When forming the conductor layer using metal foil, step (V) is preferably performed between steps (I) and (II). For example, after step (I), the support is removed, and the metal foil is laminated onto the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be legally performed using a vacuum layer. The lamination conditions can be set to be the same as those described for step (I). Next, step (II) is performed to form an insulating layer. Then, using the metal foil on the insulating layer, a conductor layer with the desired wiring pattern can be formed using known techniques such as subtractive processing or modified semi-additive processing. The metal foil can be manufactured using known methods such as electrolysis or rolling. Commercially available metal foils include, for example, HLP foil and JXUT-III foil manufactured by JX Metals Corporation, and 3EC-III foil and TP-III foil manufactured by Mitsui Mining & Metals Corporation.

[0223] When a conductor layer is formed on an insulating layer, the method for manufacturing the circuit board may include performing an annealing process after the conductor layer is formed. Annealing can improve the adhesion between the insulating layer and the conductor layer. Annealing can be performed, for example, by heating at 150°C to 210°C for 20 to 180 minutes.

[0224] In the method for manufacturing circuit boards, each of the above-mentioned processes may be performed only once or may be repeated two or more times. For example, processes (I) to (V) may be performed repeatedly to form a circuit board with a multilayer structure, such as a multilayer printed wiring board having multiple insulating layers and conductor layers.

[0225] The method for manufacturing a circuit board may further include any additional steps in combination with the steps described above. For example, the method may also include a step of placing a semiconductor chip in a manner that bonds it to a conductor layer. Specifically, when manufacturing a circuit board for a semiconductor chip package containing a semiconductor chip, the method may include a step of placing the semiconductor chip. The semiconductor chip may be placed under suitable conditions that allow the terminal electrodes of the semiconductor chip to be connected to the conductors of the conductor layer formed on the insulating layer. For example, conditions used in flip-chip mounting may be used. Furthermore, the semiconductor chip may be bonded via an insulating adhesive or by reflow soldering. Further, if necessary, the placed semiconductor chip may be filled with an underfill material. Additionally, the method may include steps such as forming a sealing layer, forming a solder resist layer, and cutting the manufactured circuit board to achieve monolithic assembly.

[0226] Examples of circuit boards include printed wiring boards and semiconductor chip packages. Examples of semiconductor chip packages include FC-CSP, MIS-BGA packages, ETS-BGA packages, Fan-out type WLP (Wafer Level Package), Fan-in type WLP, Fan-out type PLP (Panel Level Package), and Fan-in type PLP. In these semiconductor chip packages, it is preferable to use a cured product formed by curing the aforementioned resin composition to form a rewiring layer as an insulating layer. However, the circuit board is not limited to those exemplified here.

[0227] [Semiconductor Devices] The aforementioned circuit board can be used in the manufacture of semiconductor devices. Semiconductor devices include the aforementioned circuit board. Examples of semiconductor devices include various semiconductor devices used in electrical products (e.g., computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical devices, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and airplanes). Example

[0228] The following examples illustrate the invention in detail. However, the invention is not limited to these examples. In the following description, "parts" and "%" to indicate quantities refer to "parts by mass" and "% by mass," respectively, unless otherwise specified. Furthermore, the temperature and pressure conditions, unless otherwise specified, are room temperature (23°C) and atmospheric pressure (1 atm). In the following description, unless otherwise specified, "Mw" represents weight-average molecular weight, and "Mn" represents number-average molecular weight.

[0229] <Synthetic Example 1: Synthesis of Reactive Ester Resin B-1> 320 g (2.0 mol) of 2,7-dihydroxynaphthalene, 184 g (1.7 mol) of benzyl alcohol, and 5.0 g of p-toluenesulfonic acid monohydrate were added to a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. The mixture was stirred while being purged with nitrogen at room temperature. Then, the temperature was raised to 150 °C, and the mixture was stirred for 4 hours while removing the generated water distillate. After the reaction was complete, 900 g of methyl isobutyl ketone and 5.4 g of 20% sodium hydroxide aqueous solution were added for neutralization. The aqueous layer was then removed by separation, followed by three washes with 280 g of water. Methyl isobutyl ketone was removed under reduced pressure to obtain 460 g of benzyl-modified naphthalene compound (A'). The obtained benzyl-modified naphthalene compound (A') was a black solid with a hydroxyl equivalent of 180 g / eq.

[0230] In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 203.0 g of isophthaloyl chloride (2.0 mol of acyl chloride group) and 1400 g of toluene were added, and the system was subjected to nitrogen purging under reduced pressure to dissolve the compounds. Next, 72.4 g (0.67 mol) of o-cresol and 240 g of benzyl-modified naphthalene compound (A') (1.33 mol of phenolic hydroxyl group) were added, and the system was subjected to nitrogen purging under reduced pressure to dissolve the compounds. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and the system was purged with nitrogen gas. The temperature was controlled below 60°C, and 400 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. The reaction was then continued under these conditions with stirring for 1 hour.

[0231] After the reaction was completed, the mixture was allowed to stand and separated to remove the aqueous layer. Next, water was added to the toluene layer containing the reactants, and the mixture was stirred for 15 minutes. The mixture was then allowed to stand and separated to remove the aqueous layer. This process was repeated until the pH of the aqueous layer reached 7. Then, the water was removed by dehydration using a decanter to obtain an active ester resin B-1 in the form of a toluene solution containing 65% by mass of non-volatile components. The structural formula of active ester resin B-1 is as follows (where n is 0–5 and m is 0–15), and the active ester equivalent of the obtained active ester resin B-1 is 238 g / eq.

[0232] [Chemistry 8] <Synthetic Example 2: Synthesis of Reactive Ester Resin B-3> In a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, 165 g of a polymer addition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / eq., softening point 85 °C), 134 g (1.0 mol) of o-allylphenol, and 1200 g of toluene were added, and the system was subjected to nitrogen purging under reduced pressure. Next, 203 g (1.0 mol) of isophthaloyl chloride was added, and the system was subjected to nitrogen purging under reduced pressure. Then, 0.6 g of tetrabutylammonium bromide was added, and while purging with nitrogen, the system temperature was maintained below 60 °C. 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours, with stirring for 1 hour after the addition was complete. After the reaction was complete, the aqueous layer was removed by sedimentation. Water was further added to the resulting toluene layer, and the mixture was stirred for 15 minutes. The aqueous layer was then removed by sedimentation. This process was repeated until the pH of the aqueous layer reached 7. Subsequently, the non-volatile components were adjusted to 70% by mass by heating and drying to obtain the active ester resin B-3 as shown in the following formula (where each s is an independent integer greater than or equal to 0 or 1, and the average value of r calculated from the addition ratio is 1. Furthermore, the dashed lines in the chemical formula represent the structures obtained by the addition polymerization of isophthaloyl chloride and phenol, and / or the reaction of o-allylphenol). The active ester equivalent of active ester resin B-3 is 214 g / eq.

[0233] [Chemistry 9] <Synthetic Example 3: Synthesis of Maleimide Resin B-6> According to Synthesis Example 1 published by the Japan Invention Association under Patent No. 2020-500211, a MEK solution of maleimide resin B (62% by mass of non-volatile component) as shown in formula (1) was prepared. The Mw / Mn of the maleimide resin D was 1.81, and t'' in formula (1) was 1.47 (mainly 1, 2 or 3).

[0234] [Chemistry 10] <Synthesis Example 4: Synthesis of Vinyl Resin B-7> According to Example 1 of International Publication No. 2017 / 115813, 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were added to a 5.0 L reactor. 600 mmol of boron trifluoride diethyl ether complex was added at 70 °C, and the reaction was carried out for 4 hours. The polymerization solution was terminated with an aqueous sodium bicarbonate solution. The oil layer was then washed three times with pure water, and the polymer was recovered by vacuum devolatilization at 60 °C. The obtained polymer was weighed, and 896.7 g of vinyl resin B-7 was obtained by weight. The weight-average molecular weight (Mw) of vinyl resin E-1 was 41300.

[0235] <Synthesis Example 5: Synthesis of Vinyl Resin B-8> In a four-necked separable flask equipped with a stirrer, 33.85 g of 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane, 16.66 g of 4,6-dichloro-2-phenylpyrimidine, and 18.66 g of potassium carbonate were weighed and added, followed by 42.50 g of N-methyl-2-pyrrolidone. The reaction was carried out at 10.0 °C for 6 hours under a nitrogen atmosphere. After the reaction, with the container cooled to 10 °C, 8.680 g of m,p-(chloromethyl)styrene was added dropwise, and the reaction was carried out at 100 °C for 4 hours.

[0236] The resulting reaction solution was diluted with 55.0 g of N-methyl-2-pyrrolidone. After removing the salt from the resulting liquid by filtration, the solution was added to 6900 g of methanol. The precipitated solid was filtered off, washed with a small amount of methanol, filtered off again for recovery, and dried under reduced pressure at 60°C for 12 hours using a vacuum dryer to obtain vinyl resin B-8 as shown in the following formula (yield 46.55 g, yield 90%, where n is an integer from 1 to 10). The weight-average molecular weight Mw of vinyl resin B-8 is 3,400.

[0237] [Chemistry 11] <Examples 1-34 and Comparative Examples 1-6> (1) Preparation of the resin composition: Weigh and mix the components according to the formulation listed in the table below. Further mix 10 parts of MEK (methyl ethyl ketone) and 10 parts of cyclohexanone, and disperse evenly using a high-speed rotary mixer to obtain a resin composition (resin varnish). It should be noted that the formulation listed in the table below represents the amount (parts by mass) of non-volatile components.

[0238] [Table 1] [Table 2] [Table 3] [Table 4]

[0239] The details of each component listed in the table are as follows.

[0240] ・(A) Ingredient • BMI-4200: A polyimide resin comprising a dimeric diamine backbone and a fluorene backbone, as shown in the following structural formula, manufactured by Designer Molecules Inc. •SLK-2800: A polyimide resin comprising a dimeric diamine backbone and a fluorene backbone as shown in the following structural formula (where X is independently a divalent group having a dimeric diamine backbone from a dimeric diamine compound, as shown in any of the following formulas (a') to (d'), m≥0, n≥1. In formulas (a') to (d'), * denotes a bond, and the bonds m, n, p, q and the bonds shown by the dashed line are the same as the bonds m, n, p, q and the bonds shown by the dashed line in formulas (a) to (d)). Manufactured by Shin-Etsu Chemical Industry Co., Ltd. [Chemistry 12] .

[0241] • (B) Components • HP-4032-SS: Epoxy equivalent 144 g / eq., manufactured by DIC, naphthalene-type epoxy resin • NC-3000L: Epoxy equivalent 270g / eq., manufactured by Nippon Kayaku Co., Ltd., biphenyl type epoxy resin • Active ester resin B-1: Active ester group equivalent 238 g / eq., the active ester resin synthesized in Synthesis Example 1. • Active ester resin B-2: Active ester equivalent 250 g / eq., active ester resin as shown in the following formula (where n≥0). A toluene solution with 60% by mass of non-volatile components. [Chemistry 13] • Active ester resin B-3: Active ester equivalent 214 g / eq., active ester resin synthesized in Synthesis Example 2, toluene solution of 70% by mass of non-volatile components. • Active ester resin B-4: Active ester equivalent 248 g / eq., a compound shown in the following formula (where n≥0, m≥0). A toluene solution containing 70% by mass of non-volatile components. [Chemistry 14] • Active ester resin B-5: Active ester equivalent 1002 g / eq., active ester resin as shown in the following formula (where n≥0, m≥0). [Chemistry 15] • HPC-8000L-65MT: Active ester equivalent 223 g / eq., non-volatile component 65% by mass toluene / MEK solution, manufactured by DIC Corporation, active ester resin containing a dicyclopentadiene-type diphenol structure. • LA-3018-50P: Phenolic hydroxyl equivalent 151 g / eq., 50% by mass of non-volatile component in 1-methoxy-2-propanol solution, manufactured by DIC Corporation, phenolic resin. • Maleimide resin B-6: Maleimide resin B-6 synthesized in Synthesis Example 3. • MIR-3000-70MT: A toluene-MEK solution with 70% by mass of non-volatile components, manufactured by Nippon Kayaku Co., Ltd., containing a maleimide resin with the structure shown in the following formula (where n represents 1 to 100). [Chemistry 16] • BMI-689: Made by Designer Molecules Inc., an aliphatic maleimide resin. • BMI-1500: Made by Designer Molecules Inc., an aliphatic maleimide resin. • OPE-2St-1200: A toluene solution with 65% by mass of non-volatile components, manufactured by Mitsubishi Gas Chemical Co., Ltd., a styrene-based free radical polymerizable resin with a polyphenylene ether resin backbone. • Vinyl resin B-7: Resin B-6 synthesized in Synthesis Example 4. • Vinyl resin B-8: Resin B-7 synthesized in Synthesis Example 5. •SLK-2700: A resin containing imide groups that does not contain a fluorene backbone and has a dimeric diamine backbone, as shown in the following formula (where -C 36 H 70 - Each is independently a divalent group with a dimeric diamine backbone from "PRIAMINE1075", m≥0, n≥1). [Chemistry 17] .

[0242] (C) Components • SO-C2: Spherical silica surface-treated with an amino-based silane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573"), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m². 2 / g, manufactured by Admatechs.

[0243] (D) Component • YX7553BH30: Manufactured by Mitsubishi Chemical Corporation, a phenoxy resin with a fluorene backbone, containing 30% by mass of non-volatile MEK / cyclohexanone solution.

[0244] (E) Components • EXL-2655: Manufactured by DOW Corporation, an organic filler material containing rubber components.

[0245] (F) Ingredients • 1B2PZ: Manufactured by Shikoku Chemical Industry Co., Ltd., an imidazole-based curing accelerator.

[0246] (2) Manufacturing of resin sheet A: As a support, a polyethylene terephthalate film (LINTEC "AL5", 38 μm thick) with a release layer was prepared. The obtained resin composition was uniformly coated on the release layer of this support so that the thickness of the dried resin composition layer reached 40 μm. Then, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A with a resin composition layer / support layer.

[0247] <Experiment 1. Determination of Dielectric Constant and Dielectric Loss Tangent> Resin sheet A was heated in an oven at 190°C for 90 minutes to cure the resin composition layer. Then, the support was peeled off to obtain the cured resin composition layer. This cured layer was cut into samples 30 mm in length and 40 mm in width to obtain cured samples for dielectric property testing.

[0248] For the solidified samples, the dielectric constant and dielectric loss tangent were determined using a measuring apparatus (Agilent Technologies, HP8362B) at a measurement frequency of 10 GHz and a measurement temperature of 90 °C via the split cylinder method. Measurements were performed using two test pieces, and the average values ​​were calculated.

[0249] <Experiment 2. Determination of Glass Transition Temperature (Tg) and Coefficient of Linear Thermal Expansion (CTE)> Resin sheet A was cured in an oven at 190°C for 90 minutes, and then the support was peeled off to obtain a cured film. The cured film was cut into pieces 20 mm in length and 6 mm in width to obtain cured samples for measuring the coefficient of linear thermal expansion. For this cured sample, Tg and CTE were measured using a TMA apparatus (thermomechanical analysis apparatus, manufactured by RIGAKU). Specifically, after mounting the cured sample on the aforementioned apparatus, two consecutive measurements were performed under the conditions of a load of 1 g and a heating rate of 5°C / min (the first measurement was performed by heating from 25°C to 220°C, and the second measurement was performed by heating from 25°C to 250°C), and the values ​​of the second measurement were recorded.

[0250] <Experiment 3. Determination of Elongation> Resin sheet A was cured in an oven at 190°C for 90 minutes, and then the support was peeled off to obtain a cured film. The cured film was cut into dumbbell shapes as specified in JIS K 6251 Tensile Test No. 5 using a die cutter to obtain a cured sample for measuring the coefficient of linear thermal expansion. For this cured sample, a tensile test was performed using a universal testing machine (Shimadzu Autograph AGS-X-5kN) with a load sensor of 50N and a test speed of 5mm / min to determine the elongation.

[0251] <Experiment 4: Determination of the adhesion between the conductor layer and the conductor layer before and after exposure to a high temperature and high humidity environment (HAST)> (1) Lamination of resin sheet A on inner substrate As the inner layer substrate, a glass cloth substrate with copper foil on both sides and an epoxy resin double-sided copper-clad laminate was prepared (copper foil thickness 18μm, substrate thickness 0.8mm, Panasonic "R1515A"). The copper foil on this surface was roughened by etching with a micro-etching agent (MEC "CZ8101") at a copper etching depth of 1μm.

[0252] The resin sheet A obtained above was laminated onto both sides of the inner layer substrate using an intermittent vacuum pressure laminator (Nikko-Materials' CVP700 two-stage add-on laminator), with the resin composition layer of resin sheet A bonded to the inner layer substrate. The lamination was performed by depressurizing the pressure to below 13 hPa for 30 seconds, followed by pressing at 100°C and 0.74 MPa for 30 seconds.

[0253] Next, the laminated resin sheet is smoothed by hot pressing at atmospheric pressure, 100°C, and 0.5 MPa for 60 seconds. Then, the support is peeled off to obtain "intermediate multilayer I" which sequentially comprises a resin composition layer / inner substrate / resin composition layer.

[0254] (2) Stacking of copper foil Prepare a copper foil with a smooth surface (35 μm thick, manufactured by Mitsui Metals & Mining Co., Ltd., "3EC-III"). Roughen the smooth surface of the copper foil by etching with a micro-etching agent (manufactured by MEC, "CZ8401") at a copper etching depth of 0.1 μm. The resulting copper foil is called "roughened copper foil".

[0255] The roughened copper foil is laminated onto both sides of the intermediate multilayer I in such a way that the roughened surface of the copper foil is bonded to the resin composition layer of the intermediate multilayer I. This lamination is performed under the same conditions as the lamination of the resin sheet A on the inner substrate. Thereby, an "intermediate multilayer II" is obtained, which sequentially comprises roughened copper foil / resin composition layer / inner substrate / resin composition layer / roughened copper foil.

[0256] (3) Thermosetting of the resin composition layer The obtained intermediate multilayer II was heated in an oven at 100°C for 30 minutes, and then transferred to an oven at 170°C for another 30 minutes. Next, the intermediate multilayer II was removed from the oven and placed at room temperature, then further heated in an oven at 190°C for an additional 90 minutes. This process thermally cured the resin composition layer, resulting in an "evaluation substrate A" that sequentially comprises a roughened copper foil, an insulating layer as a cured resin composition layer, an inner substrate, an insulating layer as a cured resin composition layer, and a roughened copper foil. In this evaluation substrate A, the roughened copper foil corresponds to the conductor layer.

[0257] (4) Determination of the tightness with the conductor layer Using the obtained evaluation substrate A, the peel strength between the roughened copper foil and the insulating layer was measured. This peel strength measurement was performed according to JIS C6481. Specifically, the peel strength was measured using the following procedures.

[0258] A rectangular section with a width of 10 mm and a length of 100 mm was cut into the roughened copper foil of evaluation substrate A. One end of this rectangular section was peeled off and clamped using a jig (TSE AUTO COM type testing machine "AC-50C-SL"). A 35 mm long section of the rectangular section was peeled off vertically, and the peel load (kgf / cm) was measured as the peel strength. The peeling was performed at room temperature at a speed of 50 mm / min. Furthermore, after a 100-hour environmental test (HAST test) at 130°C and 85% RH, the same operation was performed to measure the peel strength.

[0259] [Table 5] [Table 6] [Table 7] [Table 8] .

Claims

1. A resin composition comprising: (A) A polyimide resin comprising either a dimericane backbone or a melamine backbone, and a fluorene backbone, and (B) Thermosetting resins.

2. The resin composition according to claim 1, wherein, (A) The end of the component has a maleimide group.

3. The resin composition according to claim 1, wherein, (A) The component further includes an anhydride skeleton.

4. The resin composition according to claim 3, wherein, The anhydride skeleton contains a skeleton derived from bisphenol A type dianhydrides.

5. The resin composition according to claim 1, wherein, (B) The component has any of the functional groups of epoxy, maleimide and styrene.

6. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (A) is 0.01% by mass or more and 10% by mass or less.

7. The resin composition according to claim 1, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (B) is 5% by mass or more and 40% by mass or less.

8. The resin composition according to claim 1, further comprising (C) an inorganic filler material.

9. The resin composition according to claim 8, wherein, When the non-volatile component in the resin composition is set to 100% by mass, the content of component (C) is 50% by mass or more and 90% by mass or less.

10. The resin composition according to claim 1, wherein, The mass ratio of component (B) to component (A), i.e., component (B) / (A) is 5 or more.

11. A resin sheet comprising a support and a resin composition layer comprising the resin composition of any one of claims 1 to 10 disposed on the support.

12. A circuit board comprising an insulating layer formed from a cured resin composition according to any one of claims 1 to 10.

13. A semiconductor device comprising the circuit board of claim 12.

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