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

Abstract

The present invention relates to a thermosetting resin composition comprising (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, and to prepregs, laminates, printed circuit boards, and semiconductor packages using the same.

Description

Technology Field

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

[0002] In line with the recent trend toward miniaturization and high performance of electronic devices, printed circuit boards (PCBs) are advancing in wiring density and integration. Consequently, there is a growing demand for improved reliability in copper-clad laminates and interlayer insulation materials for PCBs by enhancing properties such as copper foil adhesion, heat resistance (high glass transition temperature), and low thermal expansion.

[0003] Thermosetting resins are widely used in fields such as electronic components because the unique cross-linking structure of their cured products exhibits high heat resistance and dimensional stability.

[0004] Maleimide resin is known as a thermosetting resin with high heat resistance, but since maleimide resin has low curability, various studies are being conducted to improve it.

[0005] Patent Document 1 discloses a thermosetting resin composition that is capable of being molded at a relatively low temperature and, furthermore, has excellent heat resistance, water absorption characteristics, mechanical strength, and thermal decomposition characteristics after curing, comprising a compound having a maleimide group having a specific structure and a compound having an allyl group or a methacrylic group. Prior art literature

[0006] International Publication No. 2017 / 170844 The problem to be solved

[0007] However, according to the inventors' review, 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").

[0008] The objective of the present embodiment is to provide a thermosetting resin composition having good heat resistance and excellent copper foil adhesion, and a prepreg, laminate, printed circuit board, and semiconductor package using the same, in consideration of the current situation. means of solving the problem

[0009] The inventors, having conducted extensive research to solve the above problem, discovered that the problem could be solved by [1] to

[14] below and completed the present embodiment.

[0010] [1] (a) A compound having at least one N-substituted maleimide group,

[0011] (b) a compound having at least two unsaturated aliphatic hydrocarbon groups and

[0012] (c) Benzoxazine compound

[0013] A thermosetting resin composition containing

[0014] [2] The thermosetting resin composition described in [1], wherein the above (a) component comprises a reaction product of (a1) a compound having at least two N-substituted maleimide groups and (a2) a silicon compound having at least two primary amino groups.

[0015] [3] The thermosetting resin composition described in [1] or [2], wherein the above (b) component is a compound having at least three unsaturated aliphatic hydrocarbon groups.

[0016] [4] A thermosetting resin composition described in any one of [1] to [3], wherein the unsaturated aliphatic hydrocarbon group having the above (b) component is one or more selected from the group consisting of allyl groups and 1-propenyl groups.

[0017] [5] A thermosetting resin composition described in any one of [1] to [4], wherein the above (c) component is a compound represented by the following general formula (c-1).

[0018]

[0019] (during food, R c1 and R c2 Each is, independently, a hydrocarbon group having 1 to 10 carbon atoms. X c1 It is silver, 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 integers from 0 to 4.)

[0020] [6] A thermosetting resin composition described in any one of [1] to [5], wherein the content of the above (b) component is 5 to 85 parts by mass with respect to 100 parts by mass of the above (a) component.

[0021] [7] A thermosetting resin composition described in any one of [1] to [6], wherein the content of the above (c) component is 1 to 30 parts by mass per 100 parts by mass of the above (a) component.

[0022] [8] A thermosetting resin composition described in any one of [1] to [7], wherein the ratio of the content of the above (b) component and the above (c) component [(b) component / (c) component] is 1 to 15 in mass ratio.

[0023] [9] Additionally, (d) a thermosetting resin composition as a thermosetting resin, containing an epoxy resin, as described in any one of [1] to [8].

[0024]

[10] Additionally, (e) a thermosetting resin composition described in any one of [1] to [9] containing an inorganic filler.

[0025]

[11] A prepreg comprising a thermosetting resin composition as described in any of [1] to

[10] above.

[0026]

[12] A laminate made by containing the prepreg described in

[11] above.

[0027]

[13] A printed circuit board comprising the laminated board described in

[12] above.

[0028]

[14] A semiconductor package formed by mounting a semiconductor element on a printed circuit board as described in

[13] above. Effects of the invention

[0029] According to the present embodiment, a thermosetting resin composition having good heat resistance and excellent copper foil adhesion, a prepreg, a laminate, a printed circuit board, and a semiconductor package using the same can be provided. Specific details for implementing the invention

[0030] In this specification, a numerical range indicated by "to" represents a range that includes the values ​​listed before and after "to" as the minimum and maximum values, respectively.

[0031] 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. Additionally, the lower and upper limits of the numerical range may be arbitrarily combined with the lower or upper limits of other numerical ranges.

[0032] Each component and material exemplified in this specification may be used alone or in combination of two or more types, unless specifically stated otherwise.

[0033] In this specification, the content of each component in the thermosetting resin composition refers to the total amount of the plurality of substances present in the thermosetting resin composition, unless specifically stated otherwise, in cases where there are multiple substances corresponding to each component in the thermosetting resin composition.

[0034] An embodiment comprising any combination of the details described in this specification is also included in this embodiment.

[0035] The mechanisms of action described in this specification are conjectures and do not limit the mechanisms by which the thermosetting resin composition according to the present embodiment exerts its effects.

[0036] An embodiment comprising any combination of the details described in this specification is also included in this embodiment.

[0037] Additionally, in this specification, "resin component" refers to (a) component, (b) component, (c) component, and (d) component used as needed, and other optionally used resins, and (e) inorganic fillers, curing accelerators, additives, etc. are not included.

[0038] In addition, in this specification, "solids" refers to non-volatile components excluding volatile components such as organic solvents, and represents components that remain without volatilizing when the thermosetting resin composition is dried, and includes components that are liquid, syrup-like, or wax-like at room temperature.

[0039] [Thermosetting resin composition]

[0040] The thermosetting resin composition of the present embodiment is,

[0041] (a) a compound having at least one N-substituted maleimide group [hereinafter referred to as component (a)],

[0042] (b) a compound having at least two unsaturated aliphatic hydrocarbon groups [hereinafter referred to as component (b)] and

[0043] (c) Benzooxazine compound [hereinafter referred to as component (c).]

[0044] It is a thermosetting resin composition containing

[0045] The thermosetting resin composition of the present embodiment has the property that each of the above components reacts and thermosetting upon heating.

[0046] Hereinafter, each component contained in the thermosetting resin composition of the present embodiment will be described in detail.

[0047] <(a) Compounds having at least one N-substituted maleimide group>

[0048] The thermosetting resin composition of the present embodiment tends to obtain particularly excellent heat resistance and low thermal expansion by containing component (a).

[0049] (a) One type of ingredient may be used alone, or two or more types may be used in combination.

[0050] (a) As a component, (a1) a compound having at least two N-substituted maleimide groups [hereinafter referred to as component (a1)] is preferred in terms of heat resistance and low thermal expansion.

[0051] In addition, as for component (a), a reaction of component (a1) and a compound having at least two primary amino groups is preferred in terms of heat resistance, low thermal expansion and copper foil adhesion, and a reaction product of component (a1) and (a2) a silicon compound having at least two primary amino groups [hereinafter referred to as component (a2)] [hereinafter referred to as modified maleimide resin (A)] is more preferred.

[0052] ((a1) Compound having at least two N-substituted maleimide groups)

[0053] (a1) As a component, a compound represented by the following general formula (a1-1) is preferred.

[0054]

[0055] (during food, X a1 is a group represented by the following general formulas (a1-2), (a1-3), (a1-4), or (a1-5).

[0056]

[0057] (during food, R a1It is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. p1 is an integer from 0 to 4. * indicates a bonding site.)

[0058]

[0059] (during food, R a2 is, each independently, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X a2 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)-, a single bond, or a group represented by the following general formula (a1-3'). q1 is, independently, an integer from 0 to 4. * indicates a bonding site.)

[0060]

[0061] (during food, R a3 Each is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X a3 It 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. r1 is, independently, an integer from 0 to 4. * indicates a bonding site.)

[0062]

[0063] (In the formula, n1 is an integer from 1 to 10. * indicates a bonding site.)

[0064]

[0065] (during food, R a4 Each is independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. u1 is an integer from 1 to 8. * indicates a bonding site.)

[0066] In the above general formula (a1-2), R a1Examples of the aliphatic hydrocarbon groups represented by this include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-pentyl groups, etc. In addition, examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0067] p1 is an integer from 0 to 4, and from the viewpoint of availability, an integer from 0 to 2 is preferred, and 0 is more preferred. When p1 is an integer of 2 or more, a plurality of R a1 They may be the same or different.

[0068] Among the above general formula (a1-3), R a2 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by, as a halogen atom, R a1 Examples identical to the case can be cited. As for the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, a methyl group and an ethyl group are more preferred, and an ethyl group is even more preferred.

[0069] X a2 Examples of the alkylene group having 1 to 5 carbon atoms represented by α 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. Among the alkylene groups, an alkylene group having 1 to 3 carbon atoms is preferred, and a methylene group is more preferred.

[0070] X a2 Examples of the alkylidene groups having 2 to 5 carbon atoms represented by α include ethylidene groups, propylidene groups, isopropylidene groups, butylidene groups, isobutylidene groups, pentylidene groups, isopentylidene groups, etc. Among these, the isopropylidene group is preferred.

[0071] q1 is, independently, an integer from 0 to 4, and from the perspective of ease of availability, an integer from 0 to 2 is preferred, and 0 or 2 is more preferred.

[0072] Among the above general formula (a1-3'), R a3 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by this, as a halogen atom, is R a2 The same can be cited as in the case of.

[0073] X a3 As the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented here, X in the above general formula (a1-3) a2 Examples include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by.

[0074] X a3 Among the above options, an alkylidene group having 2 to 5 carbon atoms is preferred, and an isopropylidene group is more preferred.

[0075] r1 is an integer from 0 to 4, and from the perspective of ease of availability, an integer from 0 to 2 is preferred, and 0 is more preferred.

[0076] As a component (a1) used as a raw material for the modified maleimide resin (A), X of the above general formula (a1-1) is used. a1 As such, a compound having a group represented by the above general formula (a1-3) is preferred, and among them, X a2 As such, a compound having a group represented by the above general formula (a1-3') is more preferable.

[0077] In the above general formula (a1-4), n1 is an integer from 1 to 10, and from the perspective of ease of availability, an integer from 1 to 5 is preferred, and an integer from 1 to 3 is more preferred.

[0078] Among the above general formula (a1-5), R a4 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by, and as a halogen atom, R in the above general formula (a1-2). a1 The same can be cited as in the case of, and the desirable ones are also the same.

[0079] u1 is an integer from 1 to 8, preferably an integer from 1 to 3, and more preferably 1.

[0080] (a2) As a component (a1) used without reacting with the component, X of the above general formula (a1-1) a1 As such, a compound having a group represented by the above general formula (a1-4) is preferred.

[0081] (a1) As components, for example, N,N'-ethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'-[1,3-(2-methylphenylene)]bismaleimide, N,N'-[1,3-(4-methylphenylene)]bismaleimide, N,N'-(1,4-phenylene)bismaleimide, bis(4-maleimidephenyl)methane, bis(3-methyl-4-maleimidephenyl)methane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bis(4-maleimidephenyl)ether, bis(4-maleimidephenyl)sulfone, bis(4-maleimidephenyl)sulfide, bis(4-maleimidephenyl)ketone, Bis(4-maleimidecyclohexyl)methane, 1,4-bis(4-maleimidephenyl)cyclohexane, 1,4-bis(maleimidemethyl)cyclohexane, 1,4-bis(maleimidemethyl)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 1,3-bis(3-maleimidephenoxy)benzene, bis[4-(3-maleimidephenoxy)phenyl]methane, bis[4-(4-maleimidephenoxy)phenyl]methane, 1,1-bis[4-(3-maleimidephenoxy)phenyl]ethane, 1,1-bis[4-(4-maleimidephenoxy)phenyl]ethane, 1,2-bis[4-(3-maleimidephenoxy)phenyl]ethane, 1,2-Bis[4-(4-maleimidephenoxy)phenyl]ethane, 2,2-Bis[4-(3-maleimidephenoxy)phenyl]propane, 2,2-Bis[4-(4-maleimidephenoxy)phenyl]propane, 2,2-Bis[4-(3-maleimidephenoxy)phenyl]butane, 2,2-Bis[4-(4-maleimidephenoxy)phenyl]butane, 2,2-Bis[4-(3-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-Bis[4-(4-maleimidephenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 4,4'-Bis(3-maleimidephenoxy)biphenyl, 4,4'-Bis(4-maleimidephenoxy)biphenyl, bis[4-(3-maleimidephenoxy)phenyl]ketone, bis[4-(4-maleimidephenoxy)phenyl]ketone, 2,2-Bis(4-maleimidephenyl)disulfide, bis[4-(3-maleimidephenoxy)phenyl]sulfide, bis[4-(4-maleimidephenoxy)phenyl]sulfide, bis[4-(3-maleimidephenoxy)phenyl]sulfoxide,Bis[4-(4-maleimidephenoxy)phenyl]sulfoxide, Bis[4-(3-maleimidephenoxy)phenyl]sulfone, Bis[4-(4-maleimidephenoxy)phenyl]sulfone, Bis[4-(3-maleimidephenoxy)phenyl]ether, Bis[4-(4-maleimidephenoxy)phenyl]ether, 1,4-Bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-Bis[4-(4-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,4-Bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, 1,3-Bis[4-(3-maleimidephenoxy)-α,α-dimethylbenzyl]benzene, Examples include 1,4-bis[4-(4-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(3-maleimidephenoxy)-3,5-dimethyl-α,α-dimethylbenzyl]benzene, polyphenylmethanemaleimide (e.g., manufactured by Daiwa Kasei Co., Ltd., trade name: BMI-2300, etc.). (a1) One type of ingredient may be used alone, or two or more types may be used in combination.

[0082] Among these, bis(4-maleimidephenyl)methane, bis(4-maleimidephenyl)sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane are preferred in terms of high reaction rate and higher heat resistance, and 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane is more preferred.

[0083] ((a2) Silicon compound having at least two primary amino groups)

[0084] As for the component (a2) to be reacted with the component (a1) to produce a modified maleimide resin (A), a silicon compound having a primary amino group at at least one molecular end is preferred, and a silicon compound having primary amino groups at both molecular ends is more preferred. Additionally, the component (a2) may be a silicon compound having a primary amino group in a side chain, or a silicon compound having a primary amino group in a side chain and at least one molecular end.

[0085] Among these, silicon compounds having primary amino groups at both ends of the molecule are preferred. As such silicon compounds, amino-modified silicon compounds represented by the following general formula (a2-1) are preferably cited.

[0086]

[0087] (during food, R a21 Each represents, independently, an alkyl group, a phenyl group, or a substituted phenyl group. a22 and R a23 Each represents an organic group independently. n represents an integer from 2 to 50.)

[0088] In the above general formula (a2-1), R a21 As the alkyl group represented by R, an alkyl group having 1 to 5 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and an alkyl group having 1 or 2 carbon atoms is even more preferred. a21 Examples of alkyl groups represented by include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, etc., and among these, methyl groups are preferred.

[0089] R a21 Examples of substituents for the substituted phenyl group represented by are alkyl groups, alkenyl groups, alkynyl groups, etc., and among these, alkyl groups are preferred. As for the alkyl group, the same as above can be preferred.

[0090] R a21Among the groups represented by, a phenyl group or a methyl group is preferred from the perspective of solubility with other resins, and a methyl group is more preferred.

[0091] R a22 or R a23 Examples of organic groups represented by -O- include alkylene groups, alkenylene groups, alkynylene groups, arylene groups, -O-, or linkers formed by a combination thereof. Among these, substituted or unsubstituted alkylene groups and substituted or unsubstituted arylene groups are preferred, and substituted or unsubstituted alkylene groups are more preferred.

[0092] R a22 or R a23 Examples of alkylene groups represented by [this] include methylene groups, ethylene groups, trimethylene groups, etc., and trimethylene groups are preferred. In addition, examples of substituents for the alkylene groups include aryl groups having 6 to 10 carbon atoms.

[0093] R a22 or R a23 Examples of arylene groups represented by syllene groups include phenylene groups, naphthylene groups, etc. Additionally, examples of substituents for the arylene groups include alkyl groups having 1 to 5 carbon atoms.

[0094] (a2) The functional group equivalent of the component is not particularly limited, but is preferably 400 to 6,000 g / eq, more preferably 400 to 5,000 g / eq from the perspective of low thermal expansion, more preferably 450 to 3,500 g / eq, particularly preferably 500 to 1,500 g / eq, and most preferably 600 to 1,500 g / eq. Also, the functional group equivalent of the component (a2) refers to the primary amino group equivalent.

[0095] (a2) One type of ingredient may be used alone, or two or more types may be used in combination.

[0096] (a2) As for the ingredients, commercially available products may be used. As commercially available products, for example, “KF-8010” (functional group equivalent: 430g / eq), “X-22-161A” (functional group equivalent: 800g / eq), “X-22-161B” (functional group equivalent: 1,500g / eq), “KF-8012” (functional group equivalent: 2,200g / eq), “KF-8008” (functional group equivalent: 5,700g / eq), “X-22-9409” (functional group equivalent: 700g / eq), and “X-22-1660B-3” (functional group equivalent: 2,200g / eq) (all manufactured by Shinetsu Chemical Co., Ltd.), having primary amino groups at both ends. "BY-16-853U" (functional group equivalent: 460g / eq), "BY-16-853" (functional group equivalent: 650g / eq), "BY-16-853B" (functional group equivalent: 2,200g / eq) (all manufactured by Toray Dow Corning Co., Ltd.); Examples include “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 Kodo Co., Ltd., functional group equivalent: 740 g / eq), which have primary amino groups in their side chains.

[0097] Among commercially available products, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-1660B-3, BY-16-853B, and XF42-C5379 are preferred in terms of low water absorption rate, and X-22-161A, X-22-161B, KF-8012, and XF42-C5379 are preferred in terms of low thermal expansion.

[0098] (Azomethine-modified siloxane)

[0099] In addition, regarding the (a2) component, it is preferable to use one having an azomethine group for improved adhesion to copper foil and low thermal expansion, more preferable to use one having an aromatic azomethine group, and even more preferable to use an azomethine modified siloxane obtained by reacting with a dialdehyde compound [hereinafter referred to as azomethine modified siloxane (a2')]. Here, an aromatic azomethine group refers to a group in which at least one aromatic group (preferably an aromatic hydrocarbon group) is bonded to an azomethine group (-N=CH-).

[0100] Examples of the above-mentioned dialdehyde compounds 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 possess an aliphatic hydrocarbon group. For example, a molecule having a structure of aromatic hydrocarbon group - aliphatic hydrocarbon group - aromatic hydrocarbon group is also included in aromatic aldehyde compounds.

[0101] Examples of aromatic dialdehyde compounds include terephthalaldehyde, isophthalaldehyde, o-phthalaldehyde, 2,2'-bipyridine-4,4'-dicarboxyaldehyde. Among these, terephthalaldehyde may be selected from the perspective that it allows for lower thermal expansion, has high reactivity, excellent solubility in organic solvents, and is commercially available.

[0102] There are no particular limitations on the method of manufacturing the azomethine-modified siloxane (a2'), and it can be manufactured, for example, by dehydrating and condensing the amino-modified silicon compound represented by the general formula (a2-1) and the dialdehyde compound in an organic solvent. Here, the amounts of the amino-modified silicon compound represented by the general formula (a2-1) and the dialdehyde compound used are, for example, preferably 1.1 times or more than the number of primary amino groups of the amino-modified silicon compound represented by the general formula (a2-1) [amount of amino-modified silicon compound / equivalent of primary amino group of amino-modified silicon compound], more preferably 1.5 to 5 times, and even more preferably 2 to 4 times. By making the reaction 1.1 times or more, the reaction is carried out sufficiently, and the resulting azomethine-modified siloxane (a2') has primary amino groups at both ends of the molecule.

[0103] (Method for manufacturing modified maleimide resin (A))

[0104] There are no specific limitations on the method of manufacturing the modified maleimide resin (A), but for example, the modified maleimide resin (A) can be manufactured by adding a primary amino group (a2) to the carbon-carbon double bond of the maleimide group (a1).

[0105] (a) By preparing a modified maleimide resin (A) as a component, it becomes easier to control the molecular weight of the resin in the thermosetting resin composition, and excellent low thermal expansion and elastic modulus tend to be obtained.

[0106] Preferably, the preparation of the modified maleimide resin (A) is carried out in an organic solvent while maintaining the temperature. The reaction temperature is preferably 70 to 200°C, more preferably 80 to 150°C, and more preferably 100 to 130°C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 6 hours.

[0107] In the preparation of the modified maleimide resin (A), a reaction catalyst may be used as needed. Examples of reaction catalysts include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine. One type of reaction catalyst may be used alone, or two or more types may be used in combination.

[0108] In the preparation of modified maleimide resin (A), the number of maleimide groups of component (a1) [usage amount of component (a1) / functional group equivalent of maleimide group of component (a1) (g / eq)] is preferably 0.1 to 10 times the number of primary amino groups of component (a2) [usage amount of component (a2) / functional group equivalent of primary amino group of component (a2) (g / eq)], more preferably 1 to 9 times, even more preferably 1.1 to 9 times, and particularly preferably 2 to 8 times. If it is 0.1 times or more, particularly 2 times or more, gelation is suppressed and heat resistance tends to be good, and if it is 10 times or less, solubility in organic solvents and heat resistance tend to be good.

[0109] It is preferable to carry out the preparation of the modified maleimide resin (A) in the presence of an organic solvent. There are no particular limitations on the organic solvent, but examples 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-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfoxide. One type of organic solvent may be used alone, or two or more types may be used in combination. Among these, cyclohexanone, propylene glycol monomethyl ether, and methyl cellosolve are preferred in terms of solubility, cyclohexanone and propylene glycol monomethyl ether are more preferred in terms of low toxicity, and propylene glycol monomethyl ether is even more preferred in terms of high volatility and being difficult to leave as a residual solvent during the manufacture of prepreg.

[0110] The content of component (a) in the thermosetting resin composition of the present embodiment is not particularly limited, but with respect to heat resistance, low thermal expansion and copper foil adhesion, 30 to 99 parts by mass is preferred, 40 to 95 parts by mass is more preferred, 50 to 90 parts by mass is even more preferred, and 55 to 80 parts by mass is particularly preferred, with respect to 100 parts by mass of the resin component in the thermosetting resin composition.

[0111] <(b) Compounds having at least two unsaturated aliphatic hydrocarbon groups>

[0112] The thermosetting resin composition of the present embodiment tends to obtain particularly excellent heat resistance and desmear resistance by containing component (b).

[0113] (b) The ingredients may be used as a single type or in combination of two or more types.

[0114] (b) The component is preferably a compound having at least two unsaturated aliphatic hydrocarbon groups and at least three unsaturated aliphatic hydrocarbon groups, in terms of heat resistance and desmear resistance.

[0115] In addition, the unsaturated aliphatic hydrocarbon group having component (b) is not particularly limited, but it is preferable that it be an unsaturated aliphatic hydrocarbon group capable of radical reaction, and examples include vinyl group, isopropenyl group, 1-propenyl group, allyl group, 1-methylallyl group, 3-butenyl group, etc. Among these, from the perspective 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 allyl group and 1-propenyl group are even more preferred. In addition, in this embodiment, groups that have unsaturated aliphatic hydrocarbon groups in part, such as maleimide groups and (meth)acryloyl groups, but cannot be considered as unsaturated aliphatic hydrocarbon groups when viewed as a whole group, are not included in the “unsaturated aliphatic hydrocarbon groups” of component (b).

[0116] (b) As components, examples include (b1) a compound having an aromatic hydrocarbon group [hereinafter referred to as compound (b1)], (b2) a compound having a heterocyclic group [hereinafter referred to as compound (b2)], etc.

[0117] Examples of aromatic hydrocarbon groups of the above compound (b1) include benzene residues, naphthalene residues, biphenyl residues, etc. Among these, benzene residues and biphenyl residues are preferred. In addition, the term "residue" here refers to a group formed by substituting at least one of the hydrogen atoms of the aromatic ring with a group other than a hydrogen atom. Furthermore, the aromatic hydrocarbon group may have substituents such as hydroxyl groups and alkoxy groups.

[0118] Specific examples of compound (b1) include the following compounds.

[0119]

[0120] (during food, R b1 to R b3 Each is an organic group, independently. m b1 n is, independently, either 0 or 1. b1 and n b2 All represent the number of repetition units of the section enclosed in angle brackets, and each independently ranges from 1 to 100.)

[0121]

[0122] (during food, R b4 to R b7 Each is an organic group, independently. m b2 and m b3 n is, independently, either 0 or 1. b3 to n b6 All represent the number of repetition units in the section enclosed in angle brackets, and each independently ranges from 1 to 100.)

[0123]

[0124] (during food, R b8 and R b9 is, each independently, an organic group. n b7 to n b10 Each represents the number of repetition units in the section enclosed in parentheses, and is independently between 1 and 100.)

[0125] Among the above formulas, R b1 to R b9Examples of organic groups represented by α include, for instance, 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; ring-forming aryl groups having 6 to 18 carbon atoms, such as phenyl, biphenyl, and naphthyl groups; ring-forming aralkyl groups having 6 to 18 carbon atoms, such as benzyl groups; and alicyclic hydrocarbon groups having 5 to 18 carbon atoms, such as adamantyl, cyclohexyl, and cyclopentadienyl groups. Among these, R b1 , R b4 and R b6 The organic group represented here may be bonded via an interposition of -O- or -S-. R b1 to R b9 The organic group represented by is preferably, among the above options, an organic group with a large volume, for example, an alkyl group having 4 to 20 carbon atoms, a ring-forming aryl group having 6 to 18 carbon atoms, a ring-forming aralkyl group having 6 to 18 carbon atoms, a hydrocarbon group having 5 to 18 carbon atoms is more preferable, and an alkyl group having 4 to 20 carbon atoms, a ring-forming aralkyl group having 6 to 18 carbon atoms, a hydrocarbon group having 5 to 18 carbon atoms is even more preferable.

[0126] In addition, multiple Rs in one molecule b1 If this exists, multiple R b1 Each may be identical, different, or a mixture of identical and different elements may be allowed. R b2 to R b9 The same can be said about this as well.

[0127] m b1 to m b3 Each can be either 0 or 1, independently.

[0128] n b1 to n b10As for each, independently, 1 to 100 is preferred, and 3 to 30 is more preferred.

[0129] Specific examples of the above compound (b2) include, for instance, the following compounds.

[0130]

[0131] (Among the above formulas, R b10 It is an aliphatic hydrocarbon group having 2 to 18 carbon atoms that may include at least one selected from the group consisting of silver, ether groups, and hydroxyl groups.

[0132] The above R b10 As such, it is preferable that it be represented by any of the following general formulas (i) to (iii).

[0133]

[0134] (during food, p b1 represents the number of repeating units of the methylene group and is an integer from 2 to 18. p b2 represents the number of repeating units of the oxyethylene group and is 0 or 1. * is the binding site.)

[0135] The above p b1 The integer from 2 to 10 is preferred, the integer from 3 to 8 is more preferred, and the integer from 3 to 5 is even more preferred.

[0136] The above p b2 1 is preferable.

[0137] The content of component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but 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 for the sake of low thermal expansion and desmear resistance.

[0138] The content of component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but with respect to heat resistance, desmear resistance, low thermal expansion and copper foil adhesion, 2 to 80 parts by mass is preferred, 5 to 60 parts by mass is more preferred, 7 to 40 parts by mass is even more preferred, and 10 to 30 parts by mass is particularly preferred.

[0139] In addition, the content of component (b) in the thermosetting resin composition of the present embodiment is not particularly limited, but with respect to heat resistance, desmear resistance, low thermal expansion and copper foil adhesion, 5 to 85 parts by mass is preferred, 7 to 60 parts by mass is more preferred, 10 to 45 parts by mass is even more preferred, and 15 to 35 parts by mass is particularly preferred.

[0140] <(c) Benzoxazine Compound>

[0141] The thermosetting resin composition of the present embodiment contains (c) a benzoxazine compound.

[0142] In addition, the term "benzoxazine compound" in the present embodiment refers to a compound having at least one benzoxazine ring in the molecule. The term "benzoxazine ring" here includes the concept that the bonded hydrogen atom is substituted with a substituent.

[0143] The thermosetting resin composition of the present embodiment can obtain excellent copper foil adhesion while having good heat resistance by containing (c) a benzoxazine compound. Although the cause is not clear, it is presumed that the benzoxazine compound acts as a curing agent for component (a), thereby improving the degree of curing of component (a), and that the electrostatic interaction with copper is enhanced by heteroatoms derived from the benzoxazine compound.

[0144] (c) The ingredients may be used as a single type or in combination of two or more types.

[0145] (c) The number of benzoxazine rings in one molecule of the component is 1 or more, and it is more preferable to have 2 or more.

[0146] (c) As a component, known benzoxazine compounds may be used, such as Pd-type benzoxazine compounds, Fa-type benzoxazine compounds, ALP-d-type benzoxazine compounds, T-ala-type benzoxazine compounds, etc.

[0147] (c) As components, examples include compounds represented by the following general formula (c-1), compounds represented by the following general formula (c-2), compounds represented by the following general formula (c-3), etc.

[0148]

[0149] (during food, R c1 and R c2 Each is, independently, a hydrocarbon group having 1 to 10 carbon atoms. X c1 It is silver, 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 integers from 0 to 4.)

[0150]

[0151] (during food, R c3 Each is independently a hydrocarbon group having 1 to 10 carbon atoms. R c4 Each is, independently, a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. X 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.)

[0152]

[0153] (during food, R c5 is a hydrocarbon group having 1 to 10 carbon atoms. R c6 It is a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. c4 is an integer from 0 to 4.)

[0154] Among the above general formula (c-1), R c1 and R c2 Examples of hydrocarbon groups having 1 to 10 carbon atoms represented by α include aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-octyl group, n-decyl group, etc.; aromatic hydrocarbon groups such as phenyl group, etc.

[0155] Among the above general formula (c-1), n c1 and n c2 Each is independently an integer from 0 to 4, and from the viewpoint of availability, an integer from 0 to 2 is preferred, and 0 is more preferred. c1 and n c2 If is an integer greater than or equal to 2, multiple R c1 R among themselves and multiple R c2 They may be the same or different.

[0156] Among the above general formula (c-1), X c1 Examples of the alkylene groups having 1 to 5 carbon atoms shown here include methylene groups, 1,2-dimethylene groups, 1,3-trimethylene groups, 1,4-tetramethylene groups, 1,5-pentamethylene groups, etc. Among the alkylene groups, alkylene groups having 1 to 3 carbon atoms are preferred, and methylene groups are more preferred.

[0157] Among the above general formula (c-1), X c1Examples of the alkylidene groups having 2 to 5 carbon atoms shown here include ethylidene groups, propylidene groups, isopropylidene groups, butylidene groups, isobutylidene groups, pentylidene groups, isopentylidene groups, etc. Among these, the isopropylidene group is preferred.

[0158] Among the above general formula (c-2), R c3 Examples of hydrocarbon groups having 1 to 10 carbon atoms that represent this include aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-octyl group, n-decyl group, etc.; aromatic hydrocarbon groups such as phenyl group, etc.

[0159] Among the above general formula (c-2), n c3 Silver is an integer from 0 to 3, and from the perspective of ease of availability, an integer from 0 to 2 is preferred, and 0 is more preferred.

[0160] Among the above general formula (c-2), X c2 As the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by, X in the general formula (c-1) above c1 Examples include the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by this.

[0161] Among the above general formula (c-2), R c4 Examples of hydrocarbon groups having 1 to 10 carbon atoms represented by α include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl groups; and aromatic hydrocarbon groups such as phenyl and naphthyl groups. Among these, aromatic hydrocarbon groups are preferred, and phenyl groups are more preferred.

[0162] Among the above general formula (c-3), R c5Examples of hydrocarbon groups having 1 to 10 carbon atoms represented by α include aliphatic hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-octyl group, n-decyl group, etc.; aromatic hydrocarbon groups such as phenyl group, etc.

[0163] Among the above general formula (c-3), n c4 n is an integer from 0 to 4, and from the perspective of ease of availability, an integer from 0 to 2 is preferred, and 0 is more preferred. c4 If is an integer greater than or equal to 2, multiple R c5 They may be the same or different.

[0164] Among the above general formula (c-3), R c6 As the hydrocarbon group having 1 to 10 carbon atoms represented by this, R in the above general formula (c-2) c4 Examples include hydrocarbon groups having 1 to 10 carbon atoms that represent.

[0165] Among the compounds represented by any of the general formulas (c-1) to (c-3) above, the compound represented by general formula (c-1) and the compound represented by general formula (c-2) are preferred in terms of low thermal expansion and heat resistance, and the compound represented by general formula (c-1) is more preferred.

[0166] In addition, the compound represented by the general formula (c-1) is preferably the compound represented by the following formula (c-4), and the compound represented by the general formula (c-2) is preferably the compound represented by the following formula (c-5).

[0167]

[0168]

[0169] The content of component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but with respect to heat resistance, low thermal expansion, moldability and copper foil adhesion, 0.2 to 20 parts by mass is preferred, 1 to 15 parts by mass is more preferred, 1 to 10 parts by mass is even more preferred, and 1 to 8 parts by mass is particularly preferred.

[0170] In addition, the content of component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but with respect to heat resistance, low thermal expansion, moldability and copper foil adhesion, 1 to 30 parts by mass is preferred, 1 to 20 parts by mass is more preferred, 1 to 15 parts by mass is even more preferred, and 1 to 10 parts by mass is particularly preferred.

[0171] The content ratio [component (b) / component (c)] of the above component (b) and the above component (c) in the thermosetting resin composition of the present embodiment is not particularly limited, but in terms of heat resistance, low thermal expansion, moldability and copper foil adhesion, in terms of mass ratio, 1 to 15 is preferred, 1 to 10 is more preferred, and 1 to 8 is even more preferred.

[0172] <(d) Thermosetting resin>

[0173] The thermosetting resin composition of the present embodiment may additionally contain (d) a thermosetting resin [hereinafter referred to as component (d)]. By including component (d) in the thermosetting resin composition of the present embodiment, the adhesion to metal foil, particularly copper foil, can be further improved. In addition, the definition of the thermosetting resin (d) in the present embodiment is that it does not contain components (a) to (c).

[0174] (d) One type of ingredient may be used alone, or two or more types may be used in combination.

[0175] (d) As for the component, examples include epoxy resin, phenol resin (excluding the component of (b) above), unsaturated imide resin (excluding the component of (a) above), cyanate resin, isocyanate resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin (excluding the component of (b) above), dicyclopentadiene resin, silicone resin, triazine resin, melamine resin, etc., and it is preferable to select at least one type from the group consisting of these. Among these, epoxy resin is preferred from the perspective of moldability and electrical insulation, and from the perspective of improving copper foil adhesion.

[0176] Examples of epoxy resins include, for instance, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, naphthalene backbone-containing novolak type epoxy resin, stilbene type epoxy resin, triazine backbone-containing epoxy resin, fluorene backbone-containing epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenylaralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional phenols, diglycidyl ether compounds of polycyclic aromatics such as anthracene, and phosphorus-containing epoxy resins in which a phosphorus compound is introduced thereto.

[0177] Among these, from the perspective of moldability, a naphthalene backbone-containing novolak-type epoxy resin, a biphenylalalkyl-type epoxy resin, a bisphenol F-type epoxy resin, a bisphenol S-type epoxy resin, a naphthalene-type epoxy resin, and a dicyclopentadiene-type epoxy resin are more preferable, and a biphenylalalkyl-type epoxy resin is even more preferable.

[0178] When the thermosetting resin composition of the present embodiment contains (d) a thermosetting resin, the content thereof is not particularly limited, but with respect to heat resistance, low thermal expansion and copper foil adhesion, 1 to 20 parts by mass is preferred, 2 to 15 parts by mass is more preferred, and 4 to 12 parts by mass is even more preferred, with respect to 100 parts by mass of the resin component of the thermosetting resin composition.

[0179] <(e) Weapon Filler>

[0180] The thermosetting resin composition of the present embodiment may additionally contain (e) an inorganic filler [hereinafter referred to as component (e)]. By containing component (e), the thermosetting resin composition of the present embodiment becomes even more excellent in terms of low thermal expansion, desmear resistance, etc.

[0181] (e) One type of ingredient may be used alone, or two or more types may be used in combination.

[0182] (e) As for the components, examples include silica, alumina, titanium oxide, mica, beryllia, barium titaniumate, potassium titaniumate, strontium titaniumate, calcium titaniumate, 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, glass short fibers, glass fine powder, and hollow glass, and it is preferable to select at least one type from the group consisting of these. As for the glass, E glass, T glass, D glass, etc. are preferably examples.

[0183] Among these, silica is preferred in terms of dielectric properties, heat resistance, and low thermal expansion. Examples of silica include precipitated silica with a high moisture content produced by a wet method and dry-method silica containing 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 the manufacturing method. Among these, fused spherical silica is preferred in terms of low thermal expansion and fluidity when filled into a resin.

[0184] (e) The component may be surface-treated with a coupling agent. The method of surface treatment with a coupling agent may be a dry or wet surface treatment method for the inorganic filler before mixing, or a so-called integral blend treatment method in which an inorganic filler without surface treatment is mixed with another component to form a composition, and then a silane coupling agent is added to the composition.

[0185] Examples of coupling agents include silane-based coupling agents, titanate-based coupling agents, and silicon oligomers. Among these, silane-based coupling agents are preferred, and aminosilane-based coupling agents are more preferred.

[0186] (e) The average particle size of the component is not particularly limited, but is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, and even more preferably 0.1 to 1 μm.

[0187] Here, the average particle size in this embodiment is the particle size at the point corresponding to 50% of the volume when a cumulative frequency distribution curve based on particle size is obtained with the total volume of the particle set to 100%, and can be measured using a particle size distribution measuring device using a laser diffraction scattering method.

[0188] When the thermosetting resin composition of the present embodiment contains (e) an inorganic filler, the content thereof is not particularly limited, but with respect to heat resistance, low thermal expansion and copper foil adhesion, 10 to 500 parts by mass is preferred, 50 to 400 parts by mass is more preferred, 100 to 300 parts by mass is even more preferred, and 150 to 300 parts by mass is particularly preferred.

[0189] Other ingredients

[0190] The thermosetting resin composition of the present embodiment may contain, to the extent that it does not contradict the purpose of the present invention, one or more selected from the group consisting of, for example, thermoplastic resins, curing accelerators, organic fillers, flame retardants, ultraviolet absorbers, peroxides, antioxidants, photopolymerization initiators, fluorescent whitening agents, and adhesion improvers. In addition, regarding the other components thereof, one type may be used alone or two or more types may be used in combination.

[0191] 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, polyetheretherketone resin, silicone resin, tetrafluoroethylene resin, etc.

[0192] Examples of curing accelerators include imidazoles and their derivatives; organic phosphorus compounds such as phosphines and phosphonium salts, adducts of tertiary phosphines and quinones; and secondary amines, tertiary amines, quaternary ammonium salts.

[0193] Examples of organic fillers include resin fillers comprising polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc., and core-shell structured resin fillers.

[0194] Examples of flame retardants include phosphorus-based flame retardants such as aromatic phosphate ester compounds, phosphazene compounds, phosphinic acid esters, metal salts of phosphinic acid compounds, red, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; halogen-containing flame retardants containing bromine, chlorine, etc.; and inorganic flame retardants such as antimony trioxide.

[0195] Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers.

[0196] As for the peroxide, it is desirable to promote the reaction between component (a) and component (b), and examples include organic peroxides such as α,α'-di(t-butylperoxy)diisopropylbenzene.

[0197] Examples of antioxidants include hindered phenolic antioxidants and hindered amine-based antioxidants.

[0198] Examples of photopolymerization initiators include benzophenones, benzyl ketals, and thioxanthones.

[0199] Examples of fluorescent whitening agents include fluorescent whitening agents of stilbene derivatives.

[0200] Examples of adhesion enhancers include urea compounds such as urea silane, and the coupling agent mentioned above.

[0201] (Varnish)

[0202] 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 for use in the manufacture of prepregs, etc. That is, the varnish is also included in the thermosetting resin composition of the present embodiment.

[0203] Examples of organic solvents used in 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-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and sulfur-containing solvents such as dimethyl sulfoxide. One type of organic solvent may be used alone, or two or more types may be used in combination.

[0204] Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are preferred in terms of solubility, and methyl isobutyl ketone, cyclohexanone, and propylene glycol monomethyl ether are more preferred in terms of low toxicity.

[0205] The solid content concentration of the varnish is preferably 40 to 90 mass%, and more preferably 50 to 80 mass%. If the solid content concentration of the varnish is within the above range, good coating properties can be maintained, and a prepreg with an appropriate amount of thermosetting resin composition can be obtained.

[0206] [Prefrag]

[0207] The prepreg of the present embodiment comprises a thermosetting resin composition of the present embodiment, and more specifically, comprises a B-stage thermosetting resin composition.

[0208] The prepreg of the present embodiment can be manufactured, for example, by impregnating a fiber substrate with the thermosetting resin composition of the present embodiment and semi-curing (B-stage) it by heating, etc.

[0209] As the fiber substrate mentioned above, well-known materials used in laminates for various electrical insulation materials may be used. Examples of such materials 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 perspective of obtaining a substrate with excellent dielectric properties.

[0210] These fiber substrates have shapes such as woven fabrics, nonwoven fabrics, rovings, chopped strand mats, surfing mats, etc. The material and shape of the fiber substrate are selected according to the intended use and performance of the molded product, and, if necessary, a single material or a combination of two or more types of materials and shapes may be used. For example, a fiber substrate with a thickness of about 0.03 to 0.5 mm may be used. These fiber substrates are suitable in terms of heat resistance, moisture resistance, processability, etc., if they are surface-treated with a silane coupling agent or subjected to mechanical fiber opening treatment.

[0211] The prepreg of the present embodiment has, for example, an amount of thermosetting resin composition attached to a fiber substrate (content of thermosetting resin composition excluding organic solvent in the prepreg obtained) preferably 20 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 40 to 70 mass%.

[0212] The prepreg of the present embodiment can be obtained by impregnating a fiber substrate with a thermosetting resin composition, then heating and drying at a temperature of typically 100 to 200°C for 1 to 30 minutes, and semi-curing (B-stage).

[0213] [Laminated]

[0214] The laminate of the present embodiment is a laminate formed by containing the prepreg of the present embodiment.

[0215] The laminated plate of the present embodiment is obtained by laminating the prepreg of the present embodiment. Specifically, for example, it can be manufactured by preparing one sheet of the prepreg of the present embodiment or by preparing 2 to 20 sheets stacked together and laminating them in a configuration in which a metal foil, such as copper or aluminum, is placed on one or both sides thereof. By the manufacturing method, an insulating layer formed using the prepreg of the present embodiment and a metal foil placed on one or both sides thereof are obtained. The metal foil is not particularly limited as long as it is used for electrical insulating materials. Furthermore, a laminated plate having a configuration in which a metal foil is placed on one or both sides thereof is specifically referred to as a metal-attached laminated plate.

[0216] The molding conditions for manufacturing laminates can be applied, for example, to methods for laminates and multilayer plates for electrical insulation materials.

[0217] Examples of forming devices include multi-stage presses, multi-stage vacuum presses, continuous forming machines, and autoclave forming machines.

[0218] As for molding conditions, molding can be performed in the range of, 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.

[0219] In addition, a laminated board may be manufactured by combining the prepreg of the present embodiment with an inner layer wiring board and laminating it.

[0220] [Printed Wiring Board]

[0221] The printed circuit board of the present embodiment is a printed circuit board comprising a laminate of the present embodiment.

[0222] The printed circuit board of the present embodiment can be manufactured, for example, by processing the metal-attached laminate of the present embodiment into a circuit.

[0223] As circuit processing methods, known methods such as the subtractive method, full additive method, semi-additive process (SAP), and modified semi-additive process (m-SAP) may be cited. In addition, a plurality of laminated boards processed for wiring using the prepreg of the present embodiment may be stacked and heat-pressed to form a multilayer board in a single step. Subsequently, a multilayer printed circuit board may be manufactured by forming through holes or blind via holes by drilling or laser processing, and forming interlayer wiring by plating or conductive paste.

[0224] [Semiconductor Package]

[0225] The semiconductor package of the present embodiment is a semiconductor package formed by mounting a semiconductor device on a printed circuit board of the present embodiment.

[0226] The semiconductor package of the present embodiment can be manufactured by, for example, mounting a semiconductor device such as a semiconductor chip or memory at a predetermined location on a printed circuit board of the present embodiment and sealing the semiconductor device with a sealing resin or the like.

[0227] Examples

[0228] Next, the present embodiment will be described in more detail by the following examples, but these examples do not limit the present invention.

[0229] In addition, the performance of the copper-clad laminates obtained in each example was measured and evaluated by the following method.

[0230] (1) Glass transition temperature

[0231] An evaluation substrate with dimensions of 4 mm in width × 30 mm in length × 0.4 mm in thickness was fabricated by removing the copper foil by immersing a copper-clad laminate in a copper etching solution, and the glass transition temperature was measured using a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd., product name: DVE-V4). The evaluation substrate fabricated above was installed in a detector, and measurements were taken under 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, with the temperature at which the loss modulus was maximum defined as the glass transition temperature. A higher glass transition temperature indicates superior heat resistance. Additionally, if the loss modulus exceeded 360°C, it was indicated as ">360" in Table 1.

[0232] (2) Heat resistance of solder

[0233] An evaluation board was prepared by cutting a copper laminate into a square shape with sides of 25 mm, and the time until expansion occurred was measured by observing the appearance while floating the evaluation board in a solder bath at a temperature of 288°C for a maximum of 90 minutes. The evaluation results were recorded in Table 1 as “A” when no expansion was confirmed at the point of floating for 90 minutes.

[0234] (3) Thermal expansion coefficient

[0235] A 5mm × 5mm square evaluation substrate was prepared by removing the copper foil by immersing a copper-clad laminate in a copper etching solution, and thermomechanical analysis was performed using the compression method with a TMA test device (T.A. Instruments Japan Co., Ltd., TMAQ400EM). After mounting the evaluation substrate on the device, the temperature was raised to 260°C at a heating rate of 10°C / min, lowered to 10°C at a cooling rate of 10°C / min, and then raised again to 320°C at a heating rate of 10°C / min. The thermal expansion coefficient was measured a total of two times: during the first and second heating cycles. The average thermal expansion coefficient from 30°C to 100°C during the second measurement was calculated and taken as the value of the thermal expansion coefficient.

[0236] (4) Desmear resistance (measurement of weight loss after desmear treatment)

[0237] A 40mm × 40mm evaluation substrate, from which copper foil was removed by immersing a copper laminate in a copper etching solution, was 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 immersed in a mixing solution, “Concentrate Compact P” (aqueous solution of KMnO4: 60g / L and NaOH: 40g / L, manufactured by Atotech Japan Co., Ltd.), at 80°C for 20 minutes, and finally immersed in a neutralizing solution, “Reduction Sholucin 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.

[0238] The weight loss (g / m²) after desmear treatment relative to the dry weight before desmear treatment was calculated and used as an indicator of desmear resistance. The smaller the weight loss after desmear treatment, the better the desmear resistance.

[0239] (5) Inter-layer strength

[0240] An evaluation substrate with dimensions of 10 mm in width × 100 mm in length × 0.4 mm in thickness was fabricated by removing the copper foil from a copper laminate by immersing it in a copper etching solution. One end of the outermost insulating layer of the evaluation substrate was peeled off at the interface with the insulating layer to which it is laminated. The peeled portion was then grasped with a gripping tool, and the interlayer peel strength was measured when peeled in the vertical direction using a tensile testing machine. Additionally, the tensile speed was set to approximately 50 mm / min, and the measurement temperature was set to room temperature.

[0241] (6) Copper foil peel strength

[0242] An evaluation substrate was fabricated by immersing a copper laminate in a copper etching solution to form an outer copper foil with a width of 3 mm. One end of the evaluation substrate was peeled off at the interface between the outer copper layer and the insulating layer, and the copper foil peel strength was measured when the peeled portion was grasped with a gripping tool and peeled in the vertical direction using a tensile testing machine. Additionally, the tensile speed was set to approximately 50 mm / min, and the measurement temperature was set to room temperature.

[0243] [Synthetic Example 1; Synthesis of Modified Maleimide Resin (A)]

[0244] (1. Synthesis of azomethine-modified siloxane [(a2') component])

[0245] 592 parts by mass of biterminal amino-modified silicone "XF42-C5379" (product name: Momentive Performance Materials Japan Kodo Kaisha, 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 reaction vessel of 2 L volume equipped with a thermometer, a stirring device, and a moisture meter with a reflux condenser, and the reaction was carried out at 115°C for 2 hours. Afterward, the temperature was raised to 125°C, dehydrated by atmospheric pressure concentration, and an azomethine-modified siloxane-containing solution was obtained.

[0246] (2. Synthesis of modified maleimide resin (A))

[0247] 119 parts by mass (converted to solid content) of the azomethine-modified siloxane-containing solution, 161 parts by mass of 2,2-bis[4-(4-maleimidephenoxy)phenyl]propane (component (a1)) and 376 parts by mass of propylene glycol monomethyl ether were added to a reaction vessel with a volume of 2L equipped with a thermometer, a stirring device and a moisture meter with a reflux condenser, and the mixture was 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)].

[0248] [Examples 1 to 5, Comparative Examples 1 to 2]

[0249] Methyl ethyl ketone was used as a diluting solvent, and each component was mixed according to the formulation composition listed in Table 1 and stirred for 6 hours to prepare a varnish with a solid content (i.e., the content of the thermosetting resin composition excluding organic solvent) of 65 mass%.

[0250] Next, the obtained varnish was impregnated and coated onto an E glass cross with a thickness of 0.1 mm, and heated and dried at 110°C for 3 minutes to obtain a prepreg with a thermosetting resin composition content of 47 to 48 mass%.

[0251] Four sheets of this prepreg were stacked, and 12 μm electrolytic copper foils were placed on the top and bottom. The temperature was raised to 240°C at a pressure of 3.0 MPa and a heating rate of 4.0°C / min, maintained for 85 minutes, and then cooled for 30 minutes after releasing the pressure to obtain a copper-clad laminate. The above measurements and evaluations were performed using the obtained copper-clad laminate. The results are shown in Table 1.

[0252] Each component listed in Table 1 is shown below.

[0253] [(a) Component: A compound having at least one N-substituted maleimide group]

[0254] Modified maleimide resin (a-1): Modified maleimide resin (a-1) synthesized in Synthesis Example 1

[0255] [(b) Component: A compound having at least two unsaturated aliphatic hydrocarbon groups]

[0256] Allylated phenol resin: "LVA01" manufactured by Gunei Kagaku Kogyo Co., Ltd., a compound represented by the following formula (b-8).

[0257]

[0258] [(c) Ingredient: Benzoxazine compound]

[0259] 3,3'-(methylene-1,4-diphenylene)bis(3,4-dihydro-2H-1,3-benzoxazine): Pd-type benzoxazine compound, a compound represented by the above formula (c-4).

[0260] [(d) Component: Thermosetting resin]

[0261] Biphenylaralkyl type epoxy resin: Manufactured by Nippon Kayaku Co., Ltd., Product name "NC-3000-H"

[0262] [(e) Ingredient: Inorganic filler]

[0263] Fused spherical silica: Average particle size 0.5㎛

[0264]

[0265] From Table 1, it was found that Example 1, which uses the thermosetting resin composition of the present embodiment, has an equivalent glass transition temperature, solder heat resistance, and coefficient of thermal expansion compared to Comparative Example 1, which does not contain component (c), while having improved desmear resistance, interlayer peel strength, and copper foil peel strength.

[0266] In addition, it was found that Examples 2 to 5, which use the thermosetting resin composition of the present embodiment, have equivalent glass transition temperature, solder heat resistance, and thermal expansion coefficient compared to Comparative Example 2, which does not contain component (c), while having improved desmear resistance, interlayer peel strength, and copper foil peel strength.

[0267] Based on the above, it was found that the thermosetting resin composition of the present embodiment has good heat resistance and excellent copper foil adhesion. Industrial applicability

[0268] According to the thermosetting resin composition of the present embodiment, a laminated board with good heat resistance and excellent copper foil adhesion is obtained, which allows for the manufacture of high-density and high-multilayer printed circuit boards. Therefore, the thermosetting resin composition of the present embodiment is suitable for use in printed circuit boards of electronic devices used in computers, information device terminals, etc., that process large amounts of data at high speeds. In particular, it can also be used in printed circuit boards of tablet-type personal computers and notebook-type personal computers, where there is a great demand for thinness.

Claims

Claim 1 A thermosetting resin composition comprising (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 silicon compound having at least two primary amino groups, and additionally, (d) an epoxy resin as a thermosetting resin. Claim 2 A thermosetting resin composition according to claim 1, wherein the (b) component is a compound having at least three unsaturated aliphatic hydrocarbon groups. Claim 3 A thermosetting resin composition according to claim 1 or 2, wherein the unsaturated aliphatic hydrocarbon group of the component (b) is one or more selected from the group consisting of allyl groups and 1-propenyl groups. Claim 4 A thermosetting resin composition according to claim 1 or 2, wherein the (c) component is a compound represented by the following general formula (c-1). (during food, R c1 and R c2 Each is, independently, a hydrocarbon group having 1 to 10 carbon atoms. X c1 It is silver, 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 integers from 0 to 4.) Claim 5 A thermosetting resin composition according to claim 1 or 2, wherein the content of the component (b) is 5 to 85 parts by mass with respect to 100 parts by mass of the component (a). Claim 6 A thermosetting resin composition according to claim 1 or 2, wherein the content of the component (c) is 1 to 30 parts by mass with respect to 100 parts by mass of the component (a). Claim 7 A thermosetting resin composition according to claim 1 or 2, wherein the content ratio of component (b) and component (c) [component (b) / component (c)] is 1 to 15 in mass ratio. Claim 8 In claim 1 or 2, additionally, (e) a thermosetting resin composition containing an inorganic filler. Claim 9 A prepreg comprising a thermosetting resin composition as described in claim 1 or 2. Claim 10 A laminate comprising the prepreg described in paragraph 9. Claim 11 A printed circuit board comprising a laminated board as described in Clause 10. Claim 12 A semiconductor package formed by mounting a semiconductor device on a printed circuit board as described in Clause 11. Claim 13 delete Claim 14 delete

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