Thermosetting resin composition, prepreg, laminate, printed wiring board, and semiconductor package

Abstract

The present invention relates to: a thermosetting resin composition which contains (a) a compound that has at least one N-substituted maleimide group, (b) a compound that has at least two unsaturated aliphatic hydrocarbon groups, and (c) a benzoxazine compound; a prepreg which uses this thermosetting resin composition; a laminate; a printed wiring board; and a semiconductor package.

Description

[Technical field]

[0001] The present embodiment relates to a thermosetting resin composition, a prepreg, a laminate, a printed wiring board, and a semiconductor package. [Background technology]

[0002] In recent years, with the trend toward smaller electronic devices and higher performance, printed wiring boards have become more highly integrated and have higher wiring density. Accordingly, there is an increasing demand for copper-clad laminates and interlayer insulating materials for printed wiring boards to have higher reliability through improvements in copper foil adhesion, heat resistance (high glass transition temperature), low thermal expansion, etc. Thermosetting resins are widely used in the field of electronic components and the like because the crosslinked structure specific to the cured product of the thermosetting resin provides high heat resistance and dimensional stability. Maleimide resins are known as thermosetting resins having high heat resistance. However, maleimide resins have low curing properties, and various studies have been conducted to improve this property.

[0003] Patent Document 1 discloses a thermosetting resin composition that can be molded at a relatively low temperature and has excellent heat resistance, water absorption properties, mechanical strength, and thermal decomposition properties after curing. The thermosetting resin composition contains a compound having a maleimide group with a specific structure and a compound having an allyl group or a methacryl group. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2017 / 170844 Summary of the Invention [Problem to be solved by the invention]

[0005] However, according to the investigations of the present inventors, it was found that the insulating layer formed from the thermosetting resin composition of Patent Document 1 has poor adhesion to copper foil (hereinafter also referred to as "copper foil adhesion").

[0006] In view of the current situation, an object of the present embodiment is to provide a thermosetting resin composition having good heat resistance and excellent copper foil adhesion, and a prepreg, a laminate, a printed wiring board, and a semiconductor package using the same. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following [1] to

[14] , and have completed the present embodiment. [1] (a) a compound having at least one N-substituted maleimide group, (b) a compound having at least two unsaturated aliphatic hydrocarbon groups, and (c) benzoxazine compounds, A thermosetting resin composition comprising: [2] The thermosetting resin composition according to the above [1], wherein the component (a) contains a reaction product of (a1) a compound having at least two N-substituted maleimide groups and (a2) a silicone compound having at least two primary amino groups. [3] The thermosetting resin composition according to the above [1] or [2], wherein the component (b) is a compound having at least three unsaturated aliphatic hydrocarbon groups. [4] The thermosetting resin composition according to any one of the above [1] to [3], wherein the unsaturated aliphatic hydrocarbon group of the component (b) is at least one type selected from the group consisting of an allyl group and a 1-propenyl group. [5] The thermosetting resin composition according to any one of the above [1] to [4], wherein the component (c) is a compound represented by the following general formula (c-1): [ka] (In the formula, R c1 and Rc2 are each independently a hydrocarbon group having 1 to 10 carbon atoms. c1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. c1 and n c2 are each independently an integer of 0 to 4. [6] The thermosetting resin composition according to any one of the above [1] to [5], wherein the content of the component (b) is 5 to 85 parts by mass per 100 parts by mass of the component (a). [7] The thermosetting resin composition according to any one of the above [1] to [6], wherein the content of the component (c) is 1 to 30 parts by mass per 100 parts by mass of the component (a). [8] The thermosetting resin composition according to any one of the above [1] to [7], wherein the content ratio of the component (b) to the component (c) [component (b) / component (c)] is, in terms of mass ratio, 1 to 15. [9] The thermosetting resin composition according to any one of the above [1] to [8], further comprising an epoxy resin as the (d) thermosetting resin.

[10] The thermosetting resin composition according to any one of the above [1] to [9], further comprising (e) an inorganic filler.

[11] A prepreg comprising the thermosetting resin composition according to any one of the above [1] to

[10] .

[12] A laminate comprising the prepreg according to

[11] above.

[13] A printed wiring board comprising the laminate described in

[12] above.

[14] A semiconductor package comprising the printed wiring board according to

[13] above and a semiconductor element mounted thereon. Effect of the Invention

[0008] According to the present embodiment, it is possible to provide a thermosetting resin composition having good heat resistance and excellent copper foil adhesion, and a prepreg, a laminate, a printed wiring board, and a semiconductor package using the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with the values ​​shown in the examples. In addition, the lower and upper limits of the numerical ranges may be arbitrarily combined with the lower or upper limit of other numerical ranges. Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more kinds. In this specification, the content of each component in a thermosetting resin composition means, when a plurality of substances corresponding to each component are present in the thermosetting resin composition, the total amount of the plurality of substances present in the thermosetting resin composition, unless otherwise specified. Any combination of the descriptions in this specification is also included in this embodiment. The action mechanism described in this specification is merely speculation, and does not limit the mechanism by which the effect of the thermosetting resin composition according to this embodiment is exerted. Any combination of the descriptions in this specification is also included in this embodiment.

[0010] In this specification, the term "resin component" refers to the components (a), (b), and (c), as well as the component (d) used as needed, and other resins that are optionally used, but does not include inorganic fillers (e), curing accelerators, additives, etc. In addition, in this specification, the term "solid content" refers to non-volatile content excluding volatile components such as organic solvents, and refers to components that remain without volatilization when the thermosetting resin composition is dried, and includes those that are liquid, syrup-like, or wax-like at room temperature.

[0011] [Thermosetting resin composition] The thermosetting resin composition of the present embodiment is (a) a compound having at least one N-substituted maleimide group (hereinafter, sometimes referred to as component (a)); (b) a compound having at least two unsaturated aliphatic hydrocarbon groups (hereinafter, sometimes referred to as component (b)); and (c) a benzoxazine compound (hereinafter, sometimes referred to as component (c)); The thermosetting resin composition comprises: The thermosetting resin composition of the present embodiment has the property of being thermoset by reaction of the above-mentioned components upon heating. Hereinafter, each component contained in the thermosetting resin composition of the present embodiment will be described in detail.

[0012] <(a) Compound Having at Least One N-Substituted Maleimide Group> By including the component (a), the thermosetting resin composition of the present embodiment tends to exhibit particularly excellent heat resistance and low thermal expansion. The component (a) may be used alone or in combination of two or more types.

[0013] As the component (a), from the viewpoints of heat resistance and low thermal expansion, (a1) a compound having at least two N-substituted maleimide groups [hereinafter, sometimes referred to as component (a1)] is preferred. From the viewpoints of heat resistance, low thermal expansion, and copper foil adhesion, the component (a) is preferably a reaction between the component (a1) and a compound having at least two primary amino groups, and more preferably a reaction product between the component (a1) and a silicone compound (a2) having at least two primary amino groups [hereinafter sometimes referred to as the component (a2)] [hereinafter sometimes referred to as the modified maleimide resin (A)].

[0014] ((a1) Compound Having at Least Two N-Substituted Maleimide Groups) The component (a1) is preferably a compound represented by the following general formula (a1-1).

[0015] [ka] (In the formula, X a1is a group represented by the following general formula (a1-2), (a1-3), (a1-4) or (a1-5).

[0016] [ka] (In the formula, R a1 is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p1 is an integer of 0 to 4. * represents a bonding site.

[0017] [ka] (In the formula, R a2 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a2 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfide group, a sulfonyl group, a carbonyloxy group, -C(=O)-, a single bond, or a group represented by the following general formula (a1-3'). Each q1 is independently an integer of 0 to 4. * represents a bonding site.)

[0018] [ka] (In the formula, R a3 Each of X is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. a3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfide group, a sulfonyl group, a carbonyloxy group, -C(=O)- or a single bond. Each r1 is independently an integer of 0 to 4. * represents a bonding site.)

[0019] [ka] (In the formula, n1 is an integer of 1 to 10. * represents a binding site.)

[0020] [ka] (In the formula, R a4 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u1 is an integer of 1 to 8. * represents a bonding site.

[0021] In the above general formula (a1-2), R a1 Examples of the aliphatic hydrocarbon group represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. p1 is an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. When p1 is an integer of 2 or more, a plurality of R a1 They may be the same or different.

[0022] In the above general formula (a1-3), R a2 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a1 The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably an ethyl group. X a2 Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable. X a2 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. Among these, an isopropylidene group is preferable. Each q1 is independently an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 or 2 is more preferable.

[0023] In the above general formula (a1-3′), R a3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R a2 The same things can be said as in the case of X a3 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X in the above general formula (a1-3) are a2 Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (I) are the same as those represented by the formula (I). X a3 Among the above options, an alkylidene group having 2 to 5 carbon atoms is preferable, and an isopropylidene group is more preferable. r1 is an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, with 0 being more preferable. The component (a1) used as the raw material of the modified maleimide resin (A) is X in the above general formula (a1-1). a1 Among them, compounds having a group represented by the above general formula (a1-3) are preferred, and among them, X a2 As the alkyl group, a compound having a group represented by the above general formula (a1-3') is more preferable.

[0024] In the above general formula (a1-4), n1 is an integer of 1 to 10, and from the viewpoint of availability, an integer of 1 to 5 is preferable, and an integer of 1 to 3 is more preferable. In the above general formula (a1-5), R a4 The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R a1 The same can be mentioned as in the above, and the preferred ones are also the same. u1 is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1. The component (a1) used without reacting with the component (a2) is X in the above general formula (a1-1). a1 As the substituent, a compound having a group represented by the above general formula (a1-4) is preferred.

[0025] Examples of the component (a1) include N,N'-ethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-(1,3-phenylene) bismaleimide, N,N'-[1,3-(2-methylphenylene)] bismaleimide, N,N'-[1,3-(4-methylphenylene)] bismaleimide, N,N'-(1,4-phenylene) bismaleimide, bis(4-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4' -Diphenylmethane bismaleimide, bis(4-maleimidophenyl)ether, bis(4-maleimidophenyl)sulfone, bis(4-maleimidophenyl)sulfide, bis(4-maleimidophenyl)ketone, bis(4-maleimidocyclohexyl)methane, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-bis(maleimidomethyl)cyclohexane, 1,4-bis(maleimidomethyl)benzene, 1,3-bis(4-maleimidophenoxy)benzene, 1,3-bis(3-maleimido phenoxy)benzene, bis[4-(3-maleimidophenoxy)phenyl]methane, bis[4-(4-maleimidophenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidophenoxy)phenyl]ethane, 1,2-bis[4-(4-maleimidophenoxy)phenyl]ethane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]propane, 2, 2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]butane, 2,2-bis[4-(3-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-bis(3-maleimidophenoxy)biphenyl, 4,4'-Bis(4-maleimidophenoxy)biphenyl, bis[4-(3-maleimidophenoxy)phenyl]ketone, bis[4-(4-maleimidophenoxy)phenyl]ketone, 2,2-bis(4-maleimidophenyl)disulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide, bis[4-(4-maleimidophenoxy)phenyl]sulfide, bis[4-(3-maleimidophenoxy)phenyl]sulfide sulfoxide, bis[4-(4-maleimidophenoxy)phenyl]sulfoxide, bis[4-(3-maleimidophenoxy)phenyl]sulfone, bis[4-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ether, bis[4-(4-maleimidophenoxy)phenyl]ether, 1,4-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene 1,3-bis[4-(4-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4- Examples of the (a1) component include 1,4-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidophenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, and polyphenylmethane maleimide (e.g., trade name: BMI-2300, manufactured by Daiwa Kasei Co., Ltd.). One type of the (a1) component may be used alone, or two or more types may be used in combination.

[0026] Among these, from the viewpoint of high reactivity and higher heat resistance, bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane are preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane is more preferred.

[0027] ((a2) Silicone compound having at least two primary amino groups) The component (a2) to be reacted with the component (a1) to produce the modified maleimide resin (A) is preferably a silicone compound having a primary amino group at at least one molecular end, more preferably a silicone compound having primary amino groups at both molecular ends. The component (a2) may be a silicone compound having a primary amino group at the side chain, or a silicone compound having a primary amino group at the side chain and at least one molecular end. Among these, silicone compounds having primary amino groups at both molecular terminals are preferred. Preferred examples of such silicone compounds include amino-modified silicone compounds represented by the following general formula (a2-1).

[0028] [ka] (In the formula, R a21 R each independently represents an alkyl group, a phenyl group, or a substituted phenyl group. a22 and R a23 each independently represents an organic group; and n represents an integer of 2 to 50.

[0029] In the above general formula (a2-1), R a21 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and further preferably an alkyl group having 1 or 2 carbon atoms. a21Examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and among these, a methyl group is preferable. R a21 Examples of the substituent in the substituted phenyl group represented by the formula (I) include an alkyl group, an alkenyl group, an alkynyl group, etc., and among these, an alkyl group is preferable. Preferred examples of the alkyl group include the same as those described above. R a21 Among the groups represented by the formula (I), a phenyl group or a methyl group is preferred, and a methyl group is more preferred, from the viewpoint of solubility in other resins. R a22 or R a23 Examples of the organic group represented by the formula (I) include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a linking group formed by combining these groups. Among these, a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group is preferred, and a substituted or unsubstituted alkylene group is more preferred. R a22 or R a23 Examples of the alkylene group represented by the formula (I) include a methylene group, an ethylene group, a trimethylene group, etc., and a trimethylene group is preferred. Examples of the substituent of the alkylene group include an aryl group having 6 to 10 carbon atoms. R a22 or R a23 Examples of the arylene group represented by the formula (I) include a phenylene group, a naphthylene group, etc. Examples of the substituent of the arylene group include an alkyl group having 1 to 5 carbon atoms, etc.

[0030] The functional group equivalent of the (a2) component is not particularly limited, but is preferably 400 to 6,000 g / eq, and from the viewpoint of low thermal expansion, is more preferably 400 to 5,000 g / eq, further preferably 450 to 3,500 g / eq, particularly preferably 500 to 1,500 g / eq, and most preferably 600 to 1,500 g / eq. The functional group equivalent of the (a2) component means the primary amino group equivalent. The component (a2) may be used alone or in combination of two or more kinds.

[0031] As the component (a2), commercially available products can be used. Examples of commercially available products include "KF-8010" (functional group equivalent: 430 g / eq), "X-22-161A" (functional group equivalent: 800 g / eq), "X-22-161B" (functional group equivalent: 1,500 g / eq), "KF-8012" (functional group equivalent: 2,200 g / eq), "KF-8008" (functional group equivalent: 5,700 g / eq), "X-22-9409" (functional group equivalent: 700 g / eq), "X-22-1660B-3" (functional group equivalent: 2,200 g / eq) (all manufactured by Shin-Etsu Chemical Co., Ltd.), "BY-16-853U" (functional group equivalent: 460 g / eq), and "BY-16-853" (functional group equivalent: 650 g / eq), which have primary amino groups at both ends. / eq), "BY-16-853B" (functional group equivalent: 2,200 g / eq) (all manufactured by Dow Corning Toray Co., Ltd.); "KF-868" (functional group equivalent: 8,800 g / eq), "KF-865" (functional group equivalent: 5,000 g / eq), "KF-864" (functional group equivalent: 3,800 g / eq), "KF-880" (functional group equivalent: 1,800 g / eq), "KF-8004" (functional group equivalent: 1,500 g / eq) (all manufactured by Shin-Etsu Chemical Co., Ltd.), and "XF42-C5379" (trade name, manufactured by Momentive Performance Materials Japan, LLC, functional group equivalent: 740 g / eq), which have primary amino groups in the side chains, are examples. Among commercially available products, from the viewpoint of low water absorption, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, BY-16-853B, and XF42-C5379 are preferred, and from the viewpoint of low thermal expansion, X-22-161A, X-22-161B, KF-8012, and XF42-C5379 are preferred.

[0032] (Azomethine modified siloxane) Furthermore, from the viewpoints of improving adhesion to copper foil and reducing thermal expansion, it is preferable to use a component (a2) having an azomethine group, more preferably an aromatic azomethine group, and even more preferably an azomethine-modified siloxane obtained by reacting with a dialdehyde compound [hereinafter, sometimes referred to as azomethine-modified siloxane (a2')]. Here, the aromatic azomethine group refers to an azomethine group (-N=CH-) to which at least one aromatic group (preferably an aromatic hydrocarbon group) is bonded. Examples of the dialdehyde compound include aliphatic dialdehyde compounds and aromatic dialdehyde compounds. Among these, aromatic dialdehyde compounds are preferred. The aromatic dialdehyde compound has an aromatic hydrocarbon group, and may also have an aliphatic hydrocarbon group insofar as this is the case. For example, the aromatic aldehyde compound also includes a compound having a structure of aromatic hydrocarbon group-aliphatic hydrocarbon group-aromatic hydrocarbon group in the molecule.

[0033] Examples of aromatic dialdehyde compounds include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dicarboxaldehyde, etc. Among these, terephthalaldehyde may be selected from the viewpoints that it is possible to achieve a lower thermal expansion, it has high reactivity, it has excellent solubility in organic solvents, and it is commercially readily available. The method for producing the azomethine-modified siloxane (a2') is not particularly limited, and for example, the azomethine-modified siloxane (a2') can be produced by dehydration condensation reaction of the amino-modified silicone compound represented by the general formula (a2-1) and the dialdehyde compound in an organic solvent. Here, the amount of the amino-modified silicone compound represented by the general formula (a2-1) and the dialdehyde compound used is, for example, preferably 1.1 times or more, more preferably 1.5 to 5 times, and even more preferably 2 to 4 times, the number of primary amino groups of the amino-modified silicone compound represented by the general formula (a2-1) [amount of the amino-modified silicone compound used / primary amino group equivalent of the amino-modified silicone compound] of the aldehyde group of the dialdehyde compound [amount of the dialdehyde compound used / aldehyde group equivalent of the dialdehyde compound]. By making it 1.1 times or more, the reaction is sufficiently advanced, and the obtained azomethine-modified siloxane (a2') has primary amino groups at both ends of the molecule.

[0034] (Method for producing modified maleimide resin (A)) The method for producing the modified maleimide resin (A) is not particularly limited. For example, the modified maleimide resin (A) can be produced by subjecting a primary amino group in the component (a2) to an addition reaction with the carbon-carbon double bond of the maleimide group in the component (a1). By producing a modified maleimide resin (A) as the component (a), it becomes easier to control the molecular weight of the resin in the thermosetting resin composition, and excellent low thermal expansion properties and elastic modulus tend to be obtained. The modified maleimide resin (A) is preferably produced in an organic solvent while being heated and kept at a constant temperature. The reaction temperature is preferably 70 to 200° C., more preferably 80 to 150° C., and further preferably 100 to 130° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

[0035] In the production of the modified maleimide resin (A), a reaction catalyst may be used as necessary. Examples of the reaction catalyst include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. The reaction catalyst may be used alone or in combination of two or more.

[0036] In the production of the modified maleimide resin (A), the number of maleimide groups in the (a1) component [amount (g) of the (a1) component used / functional group equivalent (g / eq) of the maleimide groups in the (a1) component] is preferably 0.1 to 10 times, more preferably 1 to 9 times, even more preferably 1.1 to 9 times, and particularly preferably 2 to 8 times, the number of primary amino groups in the (a2) component [amount (g) of the (a2) component used / functional group equivalent (g / eq) of the primary amino groups in the (a2) component]. When it is 0.1 times or more, particularly 2 times or more, gelation is inhibited and heat resistance tends to be improved, while when it is 10 times or less, solubility in organic solvents and heat resistance tend to be improved.

[0037] The modified maleimide resin (A) is preferably produced in the presence of an organic solvent. The organic solvent is not particularly limited, but examples thereof include alcohol-based solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethylsulfoxide. The organic solvent may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferred, from the viewpoint of low toxicity, cyclohexanone and propylene glycol monomethyl ether are more preferred, and from the viewpoint of high volatility and less likely to remain as a residual solvent during the production of a prepreg, propylene glycol monomethyl ether is even more preferred.

[0038] The content of component (a) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion property, and copper foil adhesion, the content is preferably 30 to 99 parts by mass, more preferably 40 to 95 parts by mass, even more preferably 50 to 90 parts by mass, and particularly preferably 55 to 80 parts by mass, relative to 100 parts by mass of the resin component in the thermosetting resin composition.

[0039] <(b) Compound Having at Least Two Unsaturated Aliphatic Hydrocarbon Groups> By including the component (b), the thermosetting resin composition of the present embodiment tends to have particularly excellent heat resistance and desmear resistance. The component (b) may be used alone or in combination of two or more kinds.

[0040] From the viewpoints of heat resistance and desmear resistance, component (b) is a compound having at least two unsaturated aliphatic hydrocarbon groups, and preferably a compound having at least three unsaturated aliphatic hydrocarbon groups. The unsaturated aliphatic hydrocarbon group contained in the component (b) is not particularly limited, but is preferably an unsaturated aliphatic hydrocarbon group capable of undergoing a radical reaction, such as a vinyl group, an isopropenyl group, a 1-propenyl group, an allyl group, a 1-methylallyl group, and a 3-butenyl group. Among these, from the viewpoint of desmear resistance, an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is preferred, an unsaturated aliphatic hydrocarbon group having 2 to 5 carbon atoms is more preferred, and one or more selected from the group consisting of an allyl group and a 1-propenyl group are even more preferred. In this embodiment, a group that has an unsaturated aliphatic hydrocarbon group in a part thereof but cannot be considered as an unsaturated aliphatic hydrocarbon group when viewed as a whole, such as a maleimide group and a (meth)acryloyl group, is not included in the "unsaturated aliphatic hydrocarbon group" in the component (b).

[0041] Examples of the component (b) include (b1) a compound having an aromatic hydrocarbon group [hereinafter, sometimes referred to as compound (b1)] and (b2) a compound having a heterocyclic group [hereinafter, sometimes referred to as compound (b2)].

[0042] Examples of the aromatic hydrocarbon group contained in the compound (b1) include benzene residues, naphthalene residues, biphenyl residues, etc. Among these, benzene residues and biphenyl residues are preferred. The term "residue" as used herein means a group in which at least one of the hydrogen atoms contained in the aromatic ring is substituted with a group other than a hydrogen atom. The aromatic hydrocarbon group may have a substituent such as a hydroxyl group or an alkoxy group.

[0043] Specific examples of the compound (b1) include the following compounds.

[0044] [ka] (In the formula, R b1 ~R b3 Each of m is independently an organic group. b1 Each independently is 0 or 1. b1 and n b2 Each represents the number of repeating units of the portion surrounded by the brackets, and each independently is 1 to 100.) [ka] (In the formula, R b4 ~R b7 Each of m is independently an organic group. b2 and m b3 Each independently is 0 or 1. b3 ~n b6 Each represents the number of repeating units of the portion surrounded by the brackets, and each independently is 1 to 100.) [ka] (In the formula, R b8 and Rb9 Each of n is independently an organic group. b7 ~n b10 Each represents the number of repeating units of the portion enclosed in parentheses, and each independently is 1 to 100.)

[0045] In the above formula, R b1 ~R b9 Examples of the organic group represented by include alkyl groups having 2 to 20 carbon atoms, such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl groups; aryl groups having 6 to 18 ring carbon atoms, such as phenyl, biphenyl, and naphthyl groups; aralkyl groups having 6 to 18 ring carbon atoms, such as benzyl groups; and alicyclic hydrocarbon groups having 5 to 18 carbon atoms, such as adamantyl, cyclohexyl, and cyclopentadienyl groups. b1 , R b4 and R b6 The organic group represented by may be bonded via -O- or -S-. b1 ~R b9 Each of the organic groups represented by is preferably a bulky organic group among the above options. For example, an alkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 18 ring carbon atoms, an aralkyl group having 6 to 18 ring carbon atoms, or an alicyclic hydrocarbon group having 5 to 18 carbon atoms is more preferable, and an alkyl group having 4 to 20 carbon atoms, an aralkyl group having 6 to 18 ring carbon atoms, or an alicyclic hydrocarbon group having 5 to 18 carbon atoms is even more preferable. In addition, there are multiple R b1 If multiple R b1 may be the same or different, or may be a mixture of the same and different. b2 ~R b9 The same can be said about . m b1 ~m b3 may each independently be either 0 or 1. n b1 ~n b10Each independently is preferably 1 to 100, and more preferably 3 to 30.

[0046] Specific examples of the compound (b2) include the following compounds. [ka] (In the above formula, R b10 is an aliphatic hydrocarbon group having 2 to 18 carbon atoms which may contain at least one type selected from the group consisting of an ether group and a hydroxy group.

[0047] R b10 is preferably, for example, a group represented by any one of the following general formulas (i) to (iii). [ka] (In the formula, p b1 represents the number of repeating methylene units and is an integer from 2 to 18. b2 represents the number of repeating units of the oxyethylene group, which is 0 or 1. * is a bonding site.

[0048] The above p b1 is preferably an integer of 2 to 10, more preferably an integer of 3 to 8, and even more preferably an integer of 3 to 5. The above p b2 is preferably 1.

[0049] The content of component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of low thermal expansion and desmear resistance, it is preferable to adjust the ratio of the number of carbon-carbon double bonds in component (b) to the number of maleimide groups in component (a) [number of carbon-carbon double bonds / number of maleimide groups] to be 0.01 to 0.3.

[0050] The content of the component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance, desmear resistance, low thermal expansion property, and copper foil adhesion, the content is preferably 2 to 80 parts by mass, more preferably 5 to 60 parts by mass, even more preferably 7 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass, relative to 100 parts by mass of the resin component of the thermosetting resin composition. The content of the component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance, desmear resistance, low thermal expansion property, and copper foil adhesion, the content is preferably 5 to 85 parts by mass, more preferably 7 to 60 parts by mass, even more preferably 10 to 45 parts by mass, and particularly preferably 15 to 35 parts by mass, per 100 parts by mass of the component (a).

[0051] <(c) Benzoxazine Compound> The thermosetting resin composition of the present embodiment contains (c) a benzoxazine compound. In the present embodiment, the benzoxazine compound refers to a compound having at least one benzoxazine ring in the molecule. The benzoxazine ring in this case is a concept that includes those in which the hydrogen atom bonded to the benzoxazine ring is substituted with a substituent. The thermosetting resin composition of the present embodiment contains the benzoxazine compound (c), and thus has good heat resistance while also having excellent copper foil adhesion. The reason for this is unclear, but it is speculated that the benzoxazine compound acts as a curing agent for component (a), thereby improving the degree of curing of component (a), and that the heteroatom derived from the benzoxazine compound improves electrostatic interaction with copper, etc. The component (c) may be used alone or in combination of two or more kinds.

[0052] The number of benzoxazine rings contained in one molecule of component (c) should be one or more, and is more preferably two or more. As the component (c), a known benzoxazine compound can be used, such as a Pd-type benzoxazine compound, a Fa-type benzoxazine compound, an ALP-d-type benzoxazine compound, or a T-ala-type benzoxazine compound.

[0053] Examples of the component (c) include a compound represented by the following general formula (c-1), a compound represented by the following general formula (c-2), and a compound represented by the following general formula (c-3).

[0054] [ka] (In the formula, R c1 and R c2 are each independently a hydrocarbon group having 1 to 10 carbon atoms. c1 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. c1 and n c2 are each independently an integer of 0 to 4.

[0055] [ka] (In the formula, R c3 R is each independently a hydrocarbon group having 1 to 10 carbon atoms. c4 are each independently a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. c2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. c3 is an integer from 0 to 3.)

[0056] [ka] (In the formula, R c5 R is a hydrocarbon group having 1 to 10 carbon atoms. c6is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. c4 is an integer from 0 to 4.)

[0057] In the above general formula (c-1), R c1 and R c2 Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by include aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-octyl group, and an n-decyl group; and aromatic hydrocarbon groups such as a phenyl group. In the above general formula (c-1), n c1 and n c2 are each independently an integer of 0 to 4, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. c1 and n c2 If is an integer equal to or greater than 2, multiple R c1 R c2 They may be the same or different. In the above general formula (c-1), X c1 Examples of the alkylene group having 1 to 5 carbon atoms represented by include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, etc. As the alkylene group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable. In the above general formula (c-1), X c1 Examples of the alkylidene group having 2 to 5 carbon atoms represented by include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, an isopentylidene group, etc. Among these, an isopropylidene group is preferable.

[0058] In the above general formula (c-2), R c3 Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by include aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-octyl group, and an n-decyl group; and aromatic hydrocarbon groups such as a phenyl group. In the above general formula (c-2), n c3 is an integer of 0 to 3, and from the viewpoint of availability, an integer of 0 to 2 is preferable, and 0 is more preferable. In the above general formula (c-2), X c2 The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X in the above general formula (c-1) are c1 Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the formula (I) are the same as those represented by the formula (I). In the above general formula (c-2), R c4 Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, and n-pentyl group; and aromatic hydrocarbon groups such as phenyl group and naphthyl group. Among these, aromatic hydrocarbon groups are preferred, and phenyl group is more preferred.

[0059] In the above general formula (c-3), R c5 Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by include aliphatic hydrocarbon groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-octyl group, and an n-decyl group; and aromatic hydrocarbon groups such as a phenyl group. In the above general formula (c-3), n c4 is an integer of 0 to 4, and from the viewpoint of availability, is preferably an integer of 0 to 2, and more preferably 0. c4 If is an integer equal to or greater than 2, multiple R c5 They may be the same or different. In the above general formula (c-3), R c6 The hydrocarbon group having 1 to 10 carbon atoms represented by R in the above general formula (c-2) is c4 Examples of the hydrocarbon group include the same hydrocarbon groups having 1 to 10 carbon atoms as those represented by the formula:

[0060] Among the compounds represented by any of the above general formulas (c-1) to (c-3), from the viewpoints of low thermal expansion and heat resistance, the compounds represented by the above general formulas (c-1) and (c-2) are preferred, and the compounds represented by the above general formula (c-1) are more preferred. Furthermore, the compound represented by the above general formula (c-1) is preferably a compound represented by the following formula (c-4), and the compound represented by the above general formula (c-2) is preferably a compound represented by the following formula (c-5).

[0061] [ka]

[0062] [ka]

[0063] The content of the component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion, moldability, and copper foil adhesion, the content is preferably 0.2 to 20 parts by mass, more preferably 1 to 15 parts by mass, even more preferably 1 to 10 parts by mass, and particularly preferably 1 to 8 parts by mass, relative to 100 parts by mass of the resin component of the thermosetting resin composition. The content of the component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion, moldability, and copper foil adhesion, the content is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, even more preferably 1 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass, per 100 parts by mass of the component (a).

[0064] The content ratio of the component (b) to the component (c) in the thermosetting resin composition of the present embodiment [component (b) / component (c)] is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion property, moldability, and copper foil adhesion, the content ratio is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 8, in terms of mass ratio.

[0065] <(d) Thermosetting resin> The thermosetting resin composition of this embodiment may further contain (d) a thermosetting resin [hereinafter, sometimes referred to as component (d)]. When the thermosetting resin composition of this embodiment contains component (d), the adhesiveness to metal foils such as copper foils can be further improved. Note that the definition of the thermosetting resin (d) in this embodiment does not include components (a) to (c). The component (d) may be used alone or in combination of two or more types.

[0066] Examples of the (d) component include epoxy resins, phenolic resins (excluding the above-mentioned (b) component), unsaturated imide resins (excluding the above-mentioned (a) component), cyanate resins, isocyanate resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins (excluding the above-mentioned (b) component), dicyclopentadiene resins, silicone resins, triazine resins, melamine resins, etc., and at least one selected from the group consisting of these is preferred. Among these, epoxy resins are preferred from the viewpoints of moldability and electrical insulation, and of improving copper foil adhesion.

[0067] Examples of the epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, naphthalene skeleton-containing novolac type epoxy resins, stilbene type epoxy resins, triazine skeleton-containing epoxy resins, fluorene skeleton-containing epoxy resins, triphenolmethane type epoxy resins, biphenyl type epoxy resins, xylylene type epoxy resins, biphenyl aralkyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, alicyclic epoxy resins, polyfunctional phenols, diglycidyl ether compounds of polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins obtained by introducing a phosphorus compound into these. Among these, from the viewpoint of moldability, naphthalene skeleton-containing novolac type epoxy resins, biphenyl aralkyl type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, naphthalene type epoxy resins, and dicyclopentadiene type epoxy resins are more preferable, and biphenyl aralkyl type epoxy resins are even more preferable.

[0068] When the thermosetting resin composition of the present embodiment contains the thermosetting resin (d), the content thereof is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion property, and copper foil adhesion, the content is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, and even more preferably 4 to 12 parts by mass, relative to 100 parts by mass of the resin component of the thermosetting resin composition.

[0069] <(e) Inorganic filler> The thermosetting resin composition of the present embodiment may further contain (e) an inorganic filler (hereinafter, sometimes referred to as component (e)). When the thermosetting resin composition of the present embodiment contains component (e), the thermosetting resin composition has further excellent properties such as low thermal expansion and desmear resistance. The component (e) may be used alone or in combination of two or more types.

[0070] Examples of the component (e) include silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide, quartz powder, short glass fiber, fine glass powder, and hollow glass, and at least one selected from the group consisting of these is preferable. Examples of glass that can be used include E glass, T glass, and D glass. Among these, silica is preferred from the viewpoints of dielectric properties, heat resistance and low thermal expansion. Examples of silica include precipitated silica with high water content produced by a wet method and dry method silica with almost no bound water produced by a dry method. Dry method silica is further classified into crushed silica, fumed silica, fused spherical silica, etc., depending on the difference in production method. Among these, fused spherical silica is preferred from the viewpoints of low thermal expansion and flowability when filled into resin.

[0071] Component (e) may be surface-treated with a coupling agent. The method of surface treatment with a coupling agent may be a method of performing a dry or wet surface treatment on the inorganic filler before blending, or a so-called integral blend treatment method in which an inorganic filler without surface treatment is blended with other components to form a composition, and then a silane coupling agent is added to the composition. Examples of the coupling agent include silane-based coupling agents, titanate-based coupling agents, and silicone oligomers. Among these, silane-based coupling agents are preferred, and aminosilane-based coupling agents are more preferred.

[0072] There are no particular limitations on the average particle size of component (e), but it is preferably from 0.01 to 5 μm, more preferably from 0.05 to 3 μm, and even more preferably from 0.1 to 1 μm. Here, the average particle size in the present embodiment refers to the particle size at a point corresponding to 50% volume when a cumulative frequency distribution curve of particle sizes is calculated assuming the total volume of the particles to be 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method or the like.

[0073] When the thermosetting resin composition of the present embodiment contains the inorganic filler (e), the content thereof is not particularly limited, but from the viewpoints of heat resistance, low thermal expansion property, and copper foil adhesion, the content thereof is preferably 10 to 500 parts by mass, more preferably 50 to 400 parts by mass, even more preferably 100 to 300 parts by mass, and particularly preferably 150 to 300 parts by mass, relative to 100 parts by mass of the resin component of the thermosetting resin composition.

[0074] <Other ingredients> The thermosetting resin composition of the present embodiment may contain, for example, one or more selected from the group consisting of a thermoplastic resin, a curing accelerator, an organic filler, a flame retardant, an ultraviolet absorber, a peroxide, an antioxidant, a photopolymerization initiator, a fluorescent brightening agent, and an adhesion improver, within the scope of the object of the present invention. Note that, for each of these other components, one type may be used alone, or two or more types may be used in combination.

[0075] Examples of thermoplastic resins include polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyamideimide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyetherimide resin, polyether ether ketone resin, silicone resin, and tetrafluoroethylene resin.

[0076] Examples of the curing accelerator include imidazoles and derivatives thereof; organic phosphorus compounds such as phosphines, phosphonium salts, and adducts of tertiary phosphines and quinones; secondary amines, tertiary amines, and quaternary ammonium salts.

[0077] Examples of the organic filler include resin fillers made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., and resin fillers having a core-shell structure.

[0078] Examples of the flame retardant include phosphorus-based flame retardants such as aromatic phosphate ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate, etc.; halogen-containing flame retardants containing bromine, chlorine, etc.; and inorganic flame retardants such as antimony trioxide.

[0079] The ultraviolet ray absorbing agent may be, for example, a benzotriazole-based ultraviolet ray absorbing agent. The peroxide is preferably one that accelerates the reaction between components (a) and (b), and examples thereof include organic peroxides such as α,α'-di(t-butylperoxy)diisopropylbenzene. Examples of the antioxidant include hindered phenol-based antioxidants and hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenones, benzil ketals, and thioxanthone-based photopolymerization initiators. Examples of the fluorescent brightening agent include fluorescent brightening agents of stilbene derivatives. Examples of the adhesion improver include urea compounds such as urea silane, and the above-mentioned coupling agents.

[0080] (varnish) The thermosetting resin composition of the present embodiment may be in the form of a varnish in which each component is dissolved or dispersed in an organic solvent in order to be used for producing a prepreg, etc. In other words, the varnish is also included in the thermosetting resin composition of the present embodiment. Examples of organic solvents used in the varnish include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether-based solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethylsulfoxide. The organic solvents may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferred, and from the viewpoint of low toxicity, methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred. The solid content of the varnish is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. When the solid content of the varnish is within the above range, good coatability can be maintained and a prepreg having an appropriate amount of the thermosetting resin composition attached can be obtained.

[0081] [Prepreg] The prepreg of the present embodiment contains the thermosetting resin composition of the present embodiment, and more specifically, contains a B-staged thermosetting resin composition. The prepreg of the present embodiment can be produced, for example, by impregnating a fiber base material with the thermosetting resin composition of the present embodiment and semi-curing (B-stage) the composition by heating or the like. The fiber substrate can be any well-known material used in various electrical insulating laminates. Examples of the material include inorganic fibers such as E-glass, S-glass, low dielectric glass, and Q-glass; organic fibers such as low dielectric glass polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. In particular, low dielectric glass and Q-glass are preferred from the viewpoint of obtaining a substrate with excellent dielectric properties.

[0082] These fiber substrates have shapes such as woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. The material and shape of the fiber substrate are selected depending on the intended use, performance, etc. of the molded product, and if necessary, a single material and shape can be used or two or more types of materials and shapes can be combined. The thickness of the fiber substrate can be, for example, about 0.03 to 0.5 mm. These fiber substrates are preferably surface-treated with a silane coupling agent or mechanically opened in terms of heat resistance, moisture resistance, processability, etc.

[0083] In the prepreg of the present embodiment, for example, the adhesion amount of the thermosetting resin composition to the fiber base material (the content of the thermosetting resin composition excluding the organic solvent in the obtained prepreg) is preferably 20 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 40 to 70 mass%. The prepreg of the present embodiment can be obtained by impregnating a fiber base material with the thermosetting resin composition, and then typically drying by heating at a temperature of 100 to 200° C. for 1 to 30 minutes to semi-cure (B-stage).

[0084] [Laminate] The laminate of the present embodiment is a laminate containing the prepreg of the present embodiment. The laminate of the present embodiment is obtained by laminating and molding the prepreg of the present embodiment. Specifically, for example, one sheet of the prepreg of the present embodiment or 2 to 20 sheets of the prepreg are prepared, and a metal foil such as copper or aluminum is arranged on one or both sides of the prepreg, and laminated and molded. By this manufacturing method, a laminate having an insulating layer formed using the prepreg of the present embodiment and a metal foil arranged on one or both sides of the insulating layer is obtained. The metal foil is not particularly limited as long as it is used for electrical insulating material applications. A laminate having a configuration in which a metal foil is arranged on one or both sides of the laminate is particularly called a metal-clad laminate. The molding conditions for producing the laminated plate may be, for example, the same as those for laminated plates and multilayer plates for electrical insulating materials. Examples of molding equipment include a multi-stage press, a multi-stage vacuum press, a continuous molding machine, and an autoclave molding machine. The molding conditions may be, for example, a temperature of 100 to 250° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. Moreover, a laminate can be manufactured by combining the prepreg of this embodiment with an inner layer wiring board and laminating and molding the combined products.

[0085] [Printed wiring board] The printed wiring board of this embodiment is a printed wiring board including the laminate of this embodiment. The printed wiring board of this embodiment can be manufactured, for example, by subjecting the metal-clad laminate of this embodiment to circuit processing. Examples of the circuit processing method include known methods such as subtractive, full additive, semi-additive (SAP: Semi Additive Process), and modified semi-additive (m-SAP: modified Semi Additive Process). In addition, a plurality of laminates processed with wiring can be laminated via the prepreg of this embodiment and hot-pressed to form a multilayer structure. After that, a multilayer printed wiring board can be manufactured by forming through holes or blind via holes by drilling or laser processing and forming interlayer wiring by plating or conductive paste.

[0086] [Semiconductor package] The semiconductor package of this embodiment is a semiconductor package in which a semiconductor element is mounted on the printed wiring board of this embodiment. The semiconductor package of this embodiment can be manufactured, for example, by mounting a semiconductor element such as a semiconductor chip or memory at a predetermined position on the printed wiring board of this embodiment and sealing the semiconductor element with a sealing resin or the like. EXAMPLES

[0087] The present embodiment will now be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The copper-clad laminates obtained in each example were measured and evaluated for performance by the following methods.

[0088] (1) Glass transition temperature A copper-clad laminate was immersed in a copper etching solution to remove the copper foil, and an evaluation board with a width of 4 mm, length of 30 mm, and thickness of 0.4 mm was prepared. The glass transition temperature was measured using a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd., product name: DVE-V4). The evaluation board prepared above was attached to a detector, and measurements were performed under the measurement conditions of a heating rate of 5°C / min, a frequency of 10 Hz, and a measurement temperature range of 40 to 360°C. The temperature at which the loss modulus was maximized was taken as the glass transition temperature. The higher the glass transition temperature, the better the heat resistance. In addition, when the loss modulus exceeded 360°C, it was recorded in Table 1 as ">360".

[0089] (2) Solder heat resistance The copper-clad laminate was cut into 25 mm square pieces to prepare evaluation boards, which were then floated in a solder bath at 288°C for a maximum of 90 minutes while observing their appearance to measure the time until blistering occurred. The evaluation results are shown in Table 1, with "A" indicating that no blistering had occurred after 90 minutes of floating.

[0090] (3) Thermal expansion coefficient A 5mm x 5mm square evaluation board was prepared by removing the copper foil by immersing the copper-clad laminate in a copper etching solution, and a thermomechanical analysis was performed by the compression method using a TMA tester (TMAQ400EM, manufactured by TA Instruments Japan, Inc.). After mounting the evaluation board in the above-mentioned device, the temperature was raised to 260°C at a heating rate of 10°C / min, cooled to 10°C at a heating rate of 10°C / min, and then heated again to 320°C at a heating rate of 10°C / min. The thermal expansion coefficient was measured twice in total, during the first and second heating. The average thermal expansion coefficient from 30°C to 100°C in the second measurement was calculated, and this was used as the thermal expansion coefficient value.

[0091] (4) Desmear resistance (measurement of weight loss after desmear treatment) The copper foil was removed by immersing the copper-clad laminate in a copper etching solution to obtain a 40 mm × 40 mm evaluation board. The board was then immersed in a swelling solution, "Swelling Dip Securigant P" (aqueous solution of glycol ethers and sodium hydroxide, manufactured by Atotech Japan Co., Ltd.), at 60°C for 10 minutes, then in a roughening solution, "Concentrate Compact P" (aqueous solution of KMnO4: 60 g / L, NaOH: 40 g / L, manufactured by Atotech Japan Co., Ltd.), at 80°C for 20 minutes, and finally in a neutralizing solution, "Reduction Shoreusin Securigant P" (aqueous solution of sulfuric acid, manufactured by Atotech Japan Co., Ltd.), at 40°C for 5 minutes, and then dried at 80°C for 10 minutes to perform a desmear treatment. Weight loss after desmearing relative to dry weight before desmearing (g / m 2 The smaller the weight loss after the desmear treatment, the better the desmear resistance.

[0092] (5) Interlayer peel strength A copper-clad laminate was immersed in a copper etching solution to remove the copper foil, and an evaluation board measuring 10 mm wide x 100 mm long x 0.4 mm thick was prepared. One end of the insulating layer on the outermost surface of the evaluation board was peeled off at the interface with the insulating layer on which it was laminated, and the peeled part was held with a gripper and peeled off in the vertical direction using a tensile tester to measure the interlayer peel strength. The tensile speed was about 50 mm / min, and the measurement temperature was room temperature.

[0093] (6) Copper foil peel strength A copper-clad laminate was immersed in a copper etching solution to prepare an evaluation board with an outer copper foil of 3 mm width. One end of the evaluation board was peeled off at the interface between the outer copper layer and the insulating layer, and the peeled part was held with a gripper and peeled off in the vertical direction using a tensile tester to measure the copper foil peel strength. The tensile speed was about 50 mm / min, and the measurement temperature was room temperature.

[0094] [Synthesis Example 1: Synthesis of modified maleimide resin (A)] (1. Synthesis of azomethine-modified siloxane [component (a2')]) 592 parts by mass of "XF42-C5379" (product name, manufactured by Momentive Performance Materials Japan, LLC, functional group equivalent: 740 g / eq), 33 parts by mass of terephthalaldehyde, and 939 parts by mass of propylene glycol monomethyl ether were added to a 2 L reaction vessel equipped with a thermometer, a stirrer, and a water content meter with a reflux condenser, and reacted at 115°C for 2 hours. The mixture was then heated to 125°C and dehydrated by concentration at normal pressure to obtain a solution containing azomethine-modified siloxane. (2. Synthesis of Modified Maleimide Resin (A)) Into a 2 L reaction vessel equipped with a thermometer, a stirrer, and a moisture meter equipped with a reflux condenser, 119 parts by mass (solid content equivalent) of the above azomethine-modified siloxane-containing solution, 161 parts by mass of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane (component (a1)), and 376 parts by mass of propylene glycol monomethyl ether were added and reacted at 120° C. for 4 hours to obtain a solution containing modified maleimide resin (A) [hereinafter referred to as modified maleimide resin (a-1)].

[0095] [Examples 1 to 5, Comparative Examples 1 to 2] Using methyl ethyl ketone as a dilution solvent, the components were mixed according to the composition shown in Table 1 and then stirred for 6 hours to prepare a varnish with a solids concentration (i.e., the content of the thermosetting resin composition excluding the organic solvent) of 65 mass %. Next, the obtained varnish was applied to an E-glass cloth having a thickness of 0.1 mm for impregnation, and the cloth was dried by heating at 110° C. for 3 minutes to obtain a prepreg having a thermosetting resin composition content of 47 to 48% by mass. Four sheets of this prepreg were stacked, 12 μm electrolytic copper foil was placed on top and bottom, and the temperature was raised to 240° C. at a pressure of 3.0 MPa and a heating rate of 4.0° C. / min, and then the temperature was held for 85 minutes. After releasing the pressure, the copper-clad laminate was cooled for 30 minutes to obtain a copper-clad laminate. The above measurements and evaluations were carried out using the obtained copper-clad laminate. The results are shown in Table 1.

[0096] Each component listed in Table 1 is described below. [Component (a): Compound having at least one N-substituted maleimide group] Modified maleimide resin (a-1): Modified maleimide resin (a-1) synthesized in Synthesis Example 1

[0097] [Component (b): a compound having at least two unsaturated aliphatic hydrocarbon groups] Allylated phenol resin: "LVA01" manufactured by Gun-ei Chemical Industry Co., Ltd., a compound represented by the following formula (b-8). [ka]

[0098] [Component (c): benzoxazine compound] 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine): a Pd-type benzoxazine compound, a compound represented by the above formula (c-4)

[0099] [Component (d): Thermosetting resin] Biphenyl aralkyl type epoxy resin: Nippon Kayaku Co., Ltd., product name "NC-3000-H"

[0100] [Component (e): Inorganic filler] Fused spherical silica: average particle size 0.5 μm

[0101] [Table 1]

[0102] From Table 1, it can be seen that Example 1 using the thermosetting resin composition of this embodiment has the same glass transition temperature, solder heat resistance, and thermal expansion coefficient as Comparative Example 1 not containing the component (c), but has improved desmear resistance, interlayer peel strength, and copper foil peel strength. Moreover, it can be seen that Examples 2 to 5, which used the thermosetting resin composition of the present embodiment, have the same glass transition temperature, solder heat resistance, and thermal expansion coefficient as Comparative Example 2, which does not contain the component (c), but have improved desmear resistance, interlayer peel strength, and copper foil peel strength. From the above, it is clear that the thermosetting resin composition of the present embodiment has good heat resistance and also has excellent copper foil adhesion. [Industrial Applicability]

[0103] According to the thermosetting resin composition of the present embodiment, a laminate having good heat resistance and excellent copper foil adhesion can be obtained, so that a printed wiring board with high density and high multilayer can be manufactured. Therefore, the thermosetting resin composition of the present embodiment is suitable for use in printed wiring boards of electronic devices used in computers and information device terminals that process large amounts of data at high speed. In particular, it can be used for printed wiring boards of tablet computers and notebook computers, which are required to be thin.

Claims

1. (a) a compound having at least one N-substituted maleimide group; (b) a compound having at least two unsaturated aliphatic hydrocarbon groups, and (c) a benzoxazine compound, wherein the component (a) is a reaction product of (a1) a compound having at least two N-substituted maleimide groups and (a2) a silicone compound having at least two primary amino groups.

2. 2. The thermosetting resin composition according to claim 1, wherein the component (b) is a compound having at least three unsaturated aliphatic hydrocarbon groups.

3. 3. The thermosetting resin composition according to claim 1, wherein the unsaturated aliphatic hydrocarbon group contained in the component (b) is at least one type selected from the group consisting of an allyl group and a 1-propenyl group.

4. The thermosetting resin composition according to any one of claims 1 to 3, wherein the component (c) is a compound represented by the following general formula (c-1): 【Chemistry 1】 (In the formula, R ｃ１ and R ｃ２ are each independently a hydrocarbon group having 1 to 10 carbon atoms. ｃ１ is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, -O-, a sulfonyl group, a carbonyloxy group, -C(=O)-, or a single bond. ｃ１ and n ｃ２ are each independently an integer from 0 to 4.

5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the content of the component (b) is 5 to 85 parts by mass per 100 parts by mass of the component (a).

6. The thermosetting resin composition according to any one of claims 1 to 5, wherein the content of the component (c) is 1 to 30 parts by mass per 100 parts by mass of the component (a).

7. The thermosetting resin composition according to any one of claims 1 to 6, wherein a content ratio of the component (b) to the component (c) [component (b) / component (c)] is 1 to 15 in terms of mass ratio.

8. The thermosetting resin composition according to any one of claims 1 to 7, further comprising an epoxy resin as the thermosetting resin (d).

9. The thermosetting resin composition according to any one of claims 1 to 8, further comprising (e) an inorganic filler.

10. A prepreg comprising the thermosetting resin composition according to any one of claims 1 to 9.

11. A laminate comprising the prepreg according to claim 10.

12. A printed wiring board comprising the laminate according to claim 11.

13. A semiconductor package comprising the printed wiring board according to claim 12 and a semiconductor element mounted thereon.

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