Resin composition, prepreg, laminate, printed wiring board, and semiconductor package

Abstract

The present invention pertains to: a resin composition containing (A) a thermosetting resin, (B) a phosphorus-based flame retardant, and (C) boehmite; and a prepreg, a laminate, a printed wiring board, and a semiconductor package in each of which the resin composition is used.

Description

Resin composition, prepreg, laminate, printed wiring board, and semiconductor package

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

[0002] Conventionally, halogen-based flame retardants containing halogens such as bromine have been used as flame retardants in resin compositions used in electronic components such as printed wiring boards, semiconductor encapsulants, etc. However, in recent years, in consideration of environmental issues, the introduction of halogen-free products that do not use the conventional bromine-based flame retardants containing halogens has been promoted.

[0003] Here, "halogen-free" means that the material does not contain any halogen atoms or that the content of halogen atoms is extremely small. For example, the Japan Electronics Packaging and Circuits Association defines a halogen-free copper-clad laminate for printed wiring boards as one in which the content of chlorine (Cl) and bromine (Br) is 900 ppm or less, respectively, and the total content is 1500 ppm or less.

[0004] Therefore, currently, halogen-free flame retardants, such as phosphorus-based flame retardants such as phosphazene compounds, phosphate ester compounds, and phosphate ester amide compounds, have been proposed as flame retardants to replace halogen-containing compounds (see, for example, Patent Document 1).

[0005] JP 2023-040078 A

[0006] Although the inclusion of a phosphorus-based flame retardant in a resin composition increases flame retardancy, the copper foil adhesion, heat resistance, and desmear resistance required for printed wiring board applications tend to decrease. Therefore, it has been difficult to improve flame retardancy while maintaining good copper foil adhesion, heat resistance, and desmear resistance.

[0007] In view of the current situation, an object of the present embodiment is to provide a resin composition that has excellent flame retardancy while maintaining good copper foil adhesion, heat resistance, and desmear resistance, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package that use the resin composition.

[0008] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the present embodiment described below, and have thus completed the present embodiment. Specifically, the present embodiment relates to the following [1] to

[11] . [1] A resin composition containing (A) a thermosetting resin, (B) a phosphorus-based flame retardant, and (C) boehmite. [2] The resin composition according to [1] above, in which the content of the (C) boehmite is 1 to 25 mass% based on the total solid content (100 mass%) of the resin composition. [3] The resin composition according to [1] or [2] above, in which the content of the (B) phosphorus-based flame retardant is 1 to 25 mass% based on the total solid content (100 mass%) of the resin composition. [4] The resin composition according to any one of [1] to [3] above, wherein the ratio of the content of the (C) boehmite to the content of the (B) phosphorus-based flame retardant [(C) / (B)] is 0.1 to 15.0 by mass. [5] The resin composition according to any one of [1] to [4] above, wherein the (B) phosphorus-based flame retardant is a phosphate ester compound. [6] The resin composition according to any one of [1] to [5] above, wherein the (A) thermosetting resin contains one or more selected from the group consisting of maleimide resins and derivatives of the maleimide resins. [7] The resin composition according to any one of [1] to [6] above, further containing (D) an inorganic filler. [8] A prepreg containing the resin composition according to any one of [1] to [7] above or a semi-cured product of the resin composition. [9] A laminate having a cured product of the resin composition according to any one of [1] to [7] above and a metal foil.

[10] A printed wiring board having a cured product of the resin composition according to any one of [1] to [7] above.

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

[10] above and a semiconductor element.

[0009] According to the present embodiment, it is possible to provide a resin composition that has excellent flame retardancy while maintaining good copper foil adhesion, heat resistance, and desmear resistance, and a prepreg, a laminate, a printed wiring board, and a semiconductor package that use the resin composition.

[0010] In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. For example, a numerical range "X to Y" (X and Y are real numbers) means a numerical range that is equal to or greater than X and equal to or less than Y. In this specification, the term "X or greater" means X and a numerical value that exceeds X. In addition, the term "Y or less" in this specification means Y and a numerical value that is less than Y. The lower limit and upper limit of a numerical range described in this specification can be arbitrarily combined with the lower limit or upper limit of another numerical range. In the numerical ranges described in this specification, the lower limit or upper limit of that numerical range may be replaced with a value shown in the examples.

[0011] Unless otherwise specified, each of the components and materials exemplified in this specification may be used alone or in combination of two or more. In this specification, when a resin composition contains a plurality of substances corresponding to each component, the content of each component in the resin composition means the total amount of the plurality of substances present in the resin composition, unless otherwise specified.

[0012] In this specification, the term "solid content" refers to components other than the solvent, and components that are liquid at 25°C are also considered to be solid content.

[0013] The expression "containing XX" as used herein means both containing XX in a reacted state if XX is capable of reacting, and simply containing XX.

[0014] The weight average molecular weight (Mw) in this specification refers to a value measured in terms of polystyrene by gel permeation chromatography (GPC). Specifically, the weight average molecular weight (Mw) in this specification can be measured by the method described in the examples.

[0015] In this specification, the term "semi-cured product" is synonymous with a resin composition in a B-stage state according to JIS K 6800 (2006), and the term "cured product" is synonymous with a resin composition in a C-stage state according to JIS K 6800 (2006).

[0016] The mechanism of action described in this specification is speculation and does not limit the mechanism by which the effects of this embodiment are achieved.

[0017] Any combination of the features described in this specification is also included in this embodiment.

[0018] [Resin Composition] The resin composition of the present embodiment is a resin composition containing (A) a thermosetting resin, (B) a phosphorus-based flame retardant, and (C) boehmite. Hereinafter, each component contained in the resin composition of the present embodiment will be described in order.

[0019] <(A) Thermosetting Resin> Examples of the (A) thermosetting resin include epoxy resins, phenolic resins, maleimide resins, cyanate resins, isocyanate resins, benzoxazine resins, oxetane resins, amino resins, unsaturated polyester resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, and melamine resins. The (A) thermosetting resins may be used singly or in combination of two or more. Among these, from the viewpoints of copper foil adhesion and heat resistance, the (A) thermosetting resin preferably contains one or more selected from the group consisting of maleimide resins, epoxy resins, and cyanate resins, and more preferably contains one or more selected from the group consisting of maleimide resins and epoxy resins.

[0020] (Maleimide Resin) The resin composition of the present embodiment preferably contains, as the maleimide resin, one or more types selected from the group consisting of maleimide resins having one or more N-substituted maleimide groups and derivatives of such maleimide resins.

[0021] In the following description, a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin (AX)" or "(AX) component." Furthermore, a derivative of a maleimide resin having one or more N-substituted maleimide groups may be referred to as a "maleimide resin derivative (AY)" or "(AY) component."

[0022] (Maleimide Resin (AX)) The maleimide resin (AX) is not particularly limited as long as it is a maleimide resin having one or more N-substituted maleimide groups. From the viewpoints of copper foil adhesion and heat resistance, the maleimide resin (AX) is preferably an aromatic maleimide resin having two or more N-substituted maleimide groups, and more preferably an aromatic bismaleimide resin having two N-substituted maleimide groups.

[0023] In this specification, the term "aromatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aromatic ring. In addition, in this specification, the term "aromatic bismaleimide resin" refers to a compound having two N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, the term "aromatic polymaleimide resin" refers to a compound having three or more N-substituted maleimide groups directly bonded to an aromatic ring. In addition, in this specification, the term "aliphatic maleimide resin" refers to a compound having an N-substituted maleimide group directly bonded to an aliphatic hydrocarbon.

[0024] The maleimide resin (AX) is preferably a maleimide resin represented by the following general formula (A-1).

[0025] (In the formula, X Ａ１ is a divalent organic group.

[0026] X in the above general formula (A-1) Ａ１ Examples of the divalent organic group represented by formula (A-3), (A-4), (A-5), or (A-6) below include divalent organic groups represented by formula (A-2), (A-3), (A-4), (A-5), or (A-6) below:

[0027] (In the formula, R Ａ１ is an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Ａ１ is an integer from 0 to 4. * represents a binding site.)

[0028] R in the above general formula (A-2) Ａ１Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. n Ａ１ is an integer of 2 or more, a plurality of R Ａ１ They may be the same or different.

[0029] (In the formula, R Ａ２ and R Ａ３ are each 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, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond, or a divalent organic group represented by the following general formula (A-3-1): Ａ２ and n Ａ３ are each independently an integer of 0 to 4. * represents a binding site.

[0030] R in the above general formula (A-3) Ａ２ and R Ａ３ The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R Ａ１ The same as X in the above general formula (A-3) can be mentioned. Ａ２ Examples of the alkylene group having 1 to 5 carbon atoms represented by X include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. As the alkylene group having 1 to 5 carbon atoms, a methylene group is preferred. 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, and an isopentylidene group. Ａ２ or n Ａ３is an integer of 2 or more, a plurality of R Ａ２ R Ａ３ They may be the same or different from each other.

[0031] X in the above general formula (A-3) Ａ２ The divalent organic group represented by formula (A-3-1) is as follows:

[0032] (In the formula, R Ａ４ and R Ａ５ are each 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, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. Ａ４ and n Ａ５ are each independently an integer of 0 to 4. * represents a binding site.

[0033] R in the above general formula (A-3-1) Ａ４ and R Ａ５ The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R Ａ１ The same as X in the above general formula (A-3-1) can be mentioned. Ａ３ The alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by the above X Ａ２ The same as those in the above general formula (A-3-1) Ａ４ and n Ａ５ are each independently an integer of 0 to 4, and from the viewpoint of availability, are preferably all integers of 0 to 2. Ａ４ or n Ａ５ is an integer of 2 or more, a plurality of R Ａ４ R Ａ５ They may be the same or different from each other.

[0034] (In the formula, n Ａ６ is an integer from 0 to 10. * represents a binding site.)

[0035] (In the formula, n Ａ７is a number from 0 to 5. * represents a binding site.)

[0036] (In the formula, R Ａ６ and R Ａ７ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Ａ８ is an integer from 1 to 8. * represents a binding site.)

[0037] R in the above general formula (A-6) Ａ６ and R Ａ７ The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R Ａ１ The same as those in the general formula (A-6) above are included. Ａ８ is an integer of 2 or more, a plurality of R Ａ６ R Ａ７ They may be the same or different from each other.

[0038] Examples of the maleimide resin (AX) include aromatic bismaleimide resins, aromatic polymaleimide resins, and aliphatic maleimide resins. Among these, aromatic bismaleimide resins are preferred. That is, component (A) is preferably at least one selected from the group consisting of aromatic maleimide resins having two or more N-substituted maleimide groups and derivatives thereof. From the viewpoints of heat resistance, dielectric properties, and the like, preferred maleimide resins (AX) include bis(4-maleimidophenyl)methane, m-phenylene bismaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4-methyl-1,3-phenylene bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, aromatic bismaleimide resins having an indane skeleton, and biphenylaralkyl maleimide resins.

[0039] As the maleimide resin derivative (AY), an aminomaleimide resin having a structure derived from the above-mentioned maleimide resin (AX) and a structure derived from a diamine compound is preferred. The aminomaleimide resin can be obtained, for example, by Michael addition of the maleimide resin (AX) and a diamine compound. As the diamine compound, for example, an amine compound having at least two primary amino groups in one molecule as described in JP-A-2020-200406 can be used. Among these, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisaniline, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bisaniline, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and siloxane compounds having two primary amino groups are preferred, with siloxane compounds having two primary amino groups being more preferred. Note that, hereinafter, an aminomaleimide resin having a structure derived from a maleimide resin (AX) and a structure of a siloxane compound having two primary amino groups may be referred to as a "siloxane-modified maleimide resin."

[0040] The siloxane compound having two primary amino groups (hereinafter also referred to as "diamine-modified siloxane") is not particularly limited as long as it is a siloxane compound having two primary amino groups. The diamine-modified siloxane preferably contains a divalent group having a structure represented by the following general formula (A-7):

[0041] (In the formula, R Ａ８ and R Ａ９ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. * represents a bonding site.

[0042] R in the above general formula (A-7) Ａ８ and R Ａ９Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R include alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and n-pentyl; alkenyl groups having 2 to 5 carbon atoms; and alkynyl groups having 2 to 5 carbon atoms. The aliphatic hydrocarbon group having 1 to 5 carbon atoms may be either linear or branched. As the aliphatic hydrocarbon group having 1 to 5 carbon atoms, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, an alkyl group having 1 to 3 carbon atoms is more preferred, and a methyl group is even more preferred. R Ａ８ and R Ａ９ The substituent on the phenyl group in the substituted phenyl group represented by the formula (I) can be the above-mentioned aliphatic hydrocarbon groups having 1 to 5 carbon atoms.

[0043] The diamine-modified siloxane is preferably a silicone compound having primary amino groups at both ends, and more preferably a compound represented by the following general formula (A-8).

[0044] (In the formula, R Ａ８ and R Ａ９ is the same as in the general formula (A-7), and R Ａ１０ and R Ａ１１ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group. Ａ４ and X Ａ５ are each independently a divalent organic group, and n Ａ９ is an integer from 2 to 100.

[0045] R in the above general formula (A-8) Ａ１０ and R Ａ１１ The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R Ａ８ and R Ａ９ The same can be mentioned.

[0046] X in the above general formula (A-8) Ａ４ and X Ａ５Examples of the divalent organic group represented by include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, or a divalent linking group formed by combining these. Examples of the alkylene group include alkylene groups having 1 to 10 carbon atoms, such as a methylene group, an ethylene group, or a propylene group. Examples of the alkenylene group include alkenylene groups having 2 to 10 carbon atoms. Examples of the alkynylene group include alkynylene groups having 2 to 10 carbon atoms. Examples of the arylene group include arylene groups having 6 to 20 carbon atoms, such as a phenylene group or a naphthylene group. Among these, X Ａ４ and X Ａ５ As the alkylene group, an alkylene group or an arylene group is preferable, and an alkylene group is more preferable.

[0047] n in the above general formula (A-8) Ａ９ is an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, and even more preferably an integer of 5 to 30. Ａ９ is an integer of 2 or more, a plurality of R Ａ８ R Ａ９ They may be the same or different from each other.

[0048] The primary amino group equivalent weight of the diamine-modified siloxane is preferably 300 to 2,000 g / mol, more preferably 400 to 1,500 g / mol, and even more preferably 500 to 1,000 g / mol.

[0049] The content of the structure derived from the maleimide resin (AX) in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and even more preferably 60 to 90% by mass from the viewpoint of heat resistance. Also, the content of the structure derived from the diamine compound in the aminomaleimide resin is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and even more preferably 10 to 40% by mass from the viewpoint of low thermal expansion.

[0050] (Epoxy Resin) The epoxy resin is preferably an epoxy resin having two or more epoxy groups. One type of epoxy resin may be used alone, or two or more types may be used in combination.

[0051] Epoxy resins are classified into, for example, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, etc. Among these, glycidyl ether type epoxy resins are preferred.

[0052] Epoxy resins are classified into various epoxy resins depending on the main skeleton. Specifically, epoxy resins are classified into, for example, bisphenol-type epoxy resins such as bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins; novolac-type epoxy resins such as bisphenol A novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, biphenyl novolac-type epoxy resins, and naphthol novolac-type epoxy resins; aralkyl-type epoxy resins such as phenol aralkyl-type epoxy resins, biphenyl aralkyl-type epoxy resins, and naphthol aralkyl-type epoxy resins; stilbene-type epoxy resins; naphthylene ether-type epoxy resins; biphenyl-type epoxy resins; dihydroanthracene-type epoxy resins; epoxy resins containing a saturated dicyclopentadiene skeleton; cyclohexanedimethanol-type epoxy resins; spiro ring-containing epoxy resins; heterocyclic epoxy resins; alicyclic epoxy resins; aliphatic linear epoxy resins; and rubber-modified epoxy resins. Among these, naphthalene skeleton-containing epoxy resins are preferred from the viewpoints of heat resistance and low thermal expansion.

[0053] (Content of Component (A)) From the viewpoints of heat resistance, moldability, processability, copper foil adhesion, and dielectric properties, the content of the thermosetting resin (A) in the resin composition of the present embodiment is preferably 10 to 97 mass%, more preferably 30 to 96 mass%, even more preferably 60 to 94 mass%, and particularly preferably 80 to 92 mass%, relative to the total amount (100 mass%) of the resin components in the resin composition of the present embodiment.

[0054] From the viewpoints of heat resistance, moldability, processability, copper foil adhesion, and dielectric properties, the content of the maleimide resin in the resin composition of the present embodiment is preferably 10 to 95 mass %, more preferably 30 to 90 mass %, even more preferably 40 to 85 mass %, and particularly preferably 60 to 80 mass %, relative to the total amount (100 mass %) of the resin components in the resin composition of the present embodiment.

[0055] From the viewpoints of heat resistance, moldability, processability, copper foil adhesion, and dielectric properties, the content of the epoxy resin in the resin composition of the present embodiment is preferably 2 to 60 mass %, more preferably 5 to 50 mass %, even more preferably 8 to 40 mass %, and particularly preferably 10 to 30 mass %, relative to the total amount (100 mass %) of the resin components in the resin composition of the present embodiment.

[0056] Here, in this specification, "resin component" refers to a resin and a compound that forms a resin through a curing reaction. In the resin composition of this embodiment, for example, component (A) corresponds to the resin component. When the resin composition of this embodiment contains, as optional components, resins other than the above components or compounds that form a resin through a curing reaction, these optional components are also included in the resin component. Note that with regard to (B) phosphorus-based flame retardant, those that do not exist as particles in the cured product formed from the resin composition of this embodiment are classified as resin components, and those that exist as particles in the cured product are not classified as resin components. On the other hand, component (C) is not included in the resin component.

[0057] From the viewpoints of low thermal expansion, heat resistance, flame retardancy, and copper foil adhesion, the total content of the resin components in the resin composition of the present embodiment is preferably 10 to 70 mass%, more preferably 15 to 50 mass%, and even more preferably 20 to 40 mass%, relative to the total solid content (100 mass%) of the resin composition of the present embodiment.

[0058] <(B) Phosphorus-Based Flame Retardant> The resin composition of the present embodiment further contains (B) a phosphorus-based flame retardant. The (B) phosphorus-based flame retardant may be used alone or in combination of two or more.

[0059] The (B) phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant or an organic phosphorus-based flame retardant. From the viewpoint of reducing environmental impact, the (B) phosphorus-based flame retardant preferably does not contain halogen atoms. Examples of inorganic phosphorus-based flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide; phosphoric acid; and phosphine oxide. Examples of organic phosphorus-based flame retardants include phosphate ester compounds, monosubstituted phosphonic acid diester compounds, disubstituted phosphinic acid ester compounds, metal salts of disubstituted phosphinic acids, organic nitrogen-containing phosphorus compounds, and cyclic organic phosphorus compounds. Among these, phosphate ester compounds are preferred.

[0060] The phosphate ester compound is preferably an aromatic phosphate ester, which is a phosphate ester having an aromatic hydrocarbon group. Specific examples of the phosphate ester compound include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, 1,3-phenylene-bis(di-2,6-dimethylphenyl phosphate), 1,3-phenylene-bis(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), 1,4-phenylene-bis(di-2,6-dimethylphenyl phosphate), 4,4'-biphenylene-bis(di-2,6-dimethylphenyl phosphate), bisphenol A polyphenyl phosphate, 4,4'-biphenol-polycresyl phosphate, bisphenol A polycresyl phosphate, 4,4'-biphenol-poly(2,6-xylenyl phosphate), and bisphenol A poly(2,6-xylenyl phosphate). Of these, 1,3-phenylenebis(di-2,6-xylenyl phosphate) is preferred.

[0061] Examples of the mono-substituted phosphonic acid diester compound include divinyl phenylphosphonate, diallyl phenylphosphonate, bis(1-butenyl) phenylphosphonate, etc. Examples of the di-substituted phosphinic acid ester include phenyl diphenylphosphinate, methyl diphenylphosphinate, etc.

[0062] Examples of metal salts of disubstituted phosphinic acids include metal salts of dialkylphosphinic acids, metal salts of diallylphosphinic acids, metal salts of divinylphosphinic acids, and metal salts of diarylphosphinic acids. Examples of metal salts of disubstituted phosphinic acids include lithium salts, sodium salts, potassium salts, calcium salts, magnesium salts, aluminum salts, titanium salts, and zinc salts. Among these, aluminum salts are preferred, and aluminum trisdiethylphosphinate is more preferred.

[0063] Examples of organic nitrogen-containing phosphorus compounds include phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.

[0064] Examples of the cyclic organic phosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

[0065] (Content of Component (B)) In the resin composition of this embodiment, the content of the (B) phosphorus-based flame retardant is preferably 1 to 25 mass%, more preferably 2 to 20 mass%, even more preferably 3 to 10 mass%, and particularly preferably 3 to 7 mass%, based on the total solids content (100 mass%) of the resin composition. When the content of the (B) phosphorus-based flame retardant is equal to or greater than the above-mentioned lower limit, the flame retardancy tends to be improved. On the other hand, when the content of the (B) phosphorus-based flame retardant is equal to or less than the above-mentioned upper limit, the copper foil adhesion, heat resistance, and desmear resistance tend to be improved.

[0066] <(C) Boehmite> The resin composition of the present embodiment further contains (C) boehmite. Boehmite is alumina monohydrate, and its chemical formula is AlOOH or Al ２ O ３ ・H ２ The boehmite (C) may be used alone or in combination of two or more kinds.

[0067] Examples of the shape of (C) boehmite include plate-like, approximately rectangular, needle-like, scale-like, and spherical shapes. Among these, from the viewpoint of improving flame retardancy while maintaining good copper foil adhesion, heat resistance, and desmear resistance, plate-like or approximately rectangular shapes are preferred. In this specification, "plate-like" means that the particle thickness is 1 / 3 or less of the maximum length of the flat surface of the particle. Furthermore, the ratio of the longest side length to the shortest side length constituting the approximately rectangular shape (longest side / shortest side) is preferably 1 to 3. Note that the approximately rectangular shape includes the concept of an approximately cubic shape. The particle shape can be identified by analysis using a scanning electron microscope (SEM).

[0068] (C) Average particle diameter of boehmite (D ５０ ) is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, even more preferably 0.7 to 10 μm, and still more preferably 0.8 to 7 μm. ５０ When the average particle diameter (D) of the particles is within the above range, the copper foil adhesion, heat resistance, desmear resistance, and flame retardancy tend to be more well-balanced and excellent. ５０ The average particle diameter (D) is the particle diameter at the point corresponding to 50% volume when the cumulative frequency distribution curve of particle diameters is calculated assuming the total volume of particles to be 100%. ５０ ) can be measured, for example, by a particle size distribution measuring device using a laser diffraction scattering method.

[0069] (Content of Component (C)) In the resin composition of the present embodiment, the content of (C) boehmite is preferably 1 to 25 mass%, more preferably 3 to 20 mass%, even more preferably 4 to 15 mass%, and particularly preferably 5 to 10 mass%, of the total solid content (100 mass%) of the resin composition. When the content of (C) boehmite is within the above range, copper foil adhesion, heat resistance, desmear resistance, and flame retardancy tend to be more well-balanced and excellent.

[0070] (Content Ratio of Component (B) to Component (C)) In the resin composition of the present embodiment, the ratio of the content of the boehmite (C) to the content of the phosphorus-based flame retardant (B) [(C) / (B)], in mass ratio, is preferably 0.1 to 15.0, more preferably 0.5 to 10.0, even more preferably 0.8 to 7.0, still more preferably 1.5 to 5.0, and particularly preferably 1.7 to 3.0. When the content ratio [(C) / (B)] is within the above range, copper foil adhesion, heat resistance, desmear resistance, and flame retardancy tend to be more well-balanced and excellent.

[0071] <(D) Inorganic Filler> The resin composition of this embodiment preferably further contains (D) an inorganic filler. By containing (D) an inorganic filler, the resin composition of this embodiment tends to easily obtain better low thermal expansion and heat resistance. Note that in this embodiment, (B) a phosphorus-based flame retardant and (C) boehmite are not included in the concept of (D) inorganic filler. One type of (D) inorganic filler may be used alone, or two or more types may be used in combination.

[0072] (D) inorganic filler can be enumerated as, for example, silica, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, calcium carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide etc.Among these, from the viewpoint of low thermal expansion, heat resistance and flame retardancy, silica, mica, talc are preferred, and silica is more preferred.As silica, from the viewpoint of dispersibility and moldability, fused silica is preferred.

[0073] (D) Average particle diameter of inorganic filler (D ５０ From the viewpoint of dispersibility and fine wiring, the average particle diameter (D) of the inorganic filler (D) is preferably 0.1 to 10 μm, more preferably 0.2 to 1 μm, and even more preferably 0.3 to 0.8 μm. ５０ The average particle size of the inorganic filler (D) can be measured, for example, by a particle size distribution analyzer using a laser diffraction scattering method.

[0074] The shape of the (D) inorganic filler may be, for example, spherical or crushed, with spherical being preferred. The (D) inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent in order to improve dispersibility and adhesion to the organic component.

[0075] When the resin composition of this embodiment contains an inorganic filler (D), the content of the inorganic filler (D) is preferably 20 to 90 mass%, more preferably 30 to 80 mass%, even more preferably 40 to 70 mass%, and particularly preferably 50 to 60 mass%, based on the total solids content (100 mass%) of the resin composition. When the content of the inorganic filler (D) is equal to or greater than the above-mentioned lower limit, low thermal expansion and heat resistance tend to be more favorable. On the other hand, when the content of the inorganic filler (D) is equal to or less than the above-mentioned upper limit, moldability and copper foil adhesion tend to be more favorable.

[0076] When the resin composition of the present embodiment contains silica as the inorganic filler (D), the content of the boehmite (C) relative to 100 parts by mass of the silica is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. When the content of the boehmite (C) relative to the content of the silica is within the above range, copper foil adhesion, heat resistance, desmear resistance, low thermal expansion property, and flame retardancy tend to be more well-balanced and excellent.

[0077] <(E) Curing Accelerator> The resin composition of this embodiment preferably further contains a (E) curing accelerator. By containing the (E) curing accelerator, the resin composition of this embodiment tends to have improved curability and more excellent copper foil adhesion. One type of (E) curing accelerator may be used alone, or two or more types may be used in combination.

[0078] (E) Examples of the curing accelerator include acidic catalysts such as p-toluenesulfonic acid; amine compounds such as triethylamine, tributylamine, pyridine, and dicyandiamide; imidazole compounds such as methylimidazole, phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-cyanoethyl-2-phenylimidazolium trimellitate; isocyanate-masked imidazole compounds such as the addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole; quaternary ammonium compounds; phosphorus compounds such as triphenylphosphine; organic peroxides such as dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, and α,α'-bis(t-butylperoxy)diisopropylbenzene; and carboxylates of manganese, cobalt, zinc, and the like. Among these, isocyanate-masked imidazole compounds are preferred from the viewpoints of curing acceleration effect and storage stability.

[0079] When the resin composition of this embodiment contains a (E) curing accelerator, the content of the (E) curing accelerator is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of resin components in the resin composition. When the content of the (E) curing accelerator is equal to or greater than the above-mentioned lower limit, a sufficient curing acceleration effect tends to be easily obtained. Furthermore, when the content of the (E) curing accelerator is equal to or less than the above-mentioned upper limit, storage stability tends to be more easily improved.

[0080] <Other Optional Components> The resin composition of this embodiment may further contain, as necessary, one or more optional components selected from the group consisting of resin materials other than the above components, antioxidants, heat stabilizers, antistatic agents, UV absorbers, pigments, colorants, lubricants, organic solvents, and other additives. Each of the above optional components may be used alone, or two or more may be used in combination. The content of the above optional components in the resin composition of this embodiment is not particularly limited, and they may be used as needed within a range that does not impair the effects of this embodiment. Furthermore, the resin composition of this embodiment may not contain the above optional components depending on the desired performance.

[0081] (Organic Solvent) The resin composition of the present embodiment may contain an organic solvent from the viewpoint of ease of handling. Examples of organic solvents 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 hydrocarbon-based solvents such as toluene, xylene, and mesitylene; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfoxide; and ester-based solvents such as γ-butyrolactone. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, nitrogen-containing solvents, and aromatic hydrocarbon-based solvents are preferred, aromatic hydrocarbon-based solvents are more preferred, and toluene is even more preferred.

[0082] <Method for producing resin composition> The resin composition of this embodiment can be produced by mixing the respective components. At this time, the respective components may be dissolved or dispersed while stirring. The conditions such as the mixing order, temperature, and time are not particularly limited and may be set as desired depending on the types of raw materials, etc.

[0083] <Glass transition temperature of cured product of resin composition> From the viewpoint of heat resistance, the glass transition temperature of the cured product of the resin composition of this embodiment is preferably 200° C. or higher, more preferably 250° C. or higher, and even more preferably 300° C. or higher. The glass transition temperature of the cured product of the resin composition of this embodiment may be 400° C. or lower, or may be 350° C. or lower. The glass transition temperature of the cured product of the resin composition of this embodiment can be measured by the method described in the examples.

[0084] The flaming combustion time according to UL-94 of the cured product of the resin composition of this embodiment is preferably 5.5 seconds or less, more preferably 5.0 seconds or less, even more preferably 4.5 seconds or less, and even more preferably 4.0 seconds or less. The flaming combustion time may be 1.0 second or more, 2.0 seconds or more, or even 3.0 seconds or more. The flaming combustion time according to UL-94 can be measured by the method described in the examples.

[0085] [Prepreg] The prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment or a semi-cured product of the resin composition. The prepreg of the present embodiment contains, for example, the resin composition of the present embodiment or a semi-cured product of the resin composition and a sheet-like fiber base material.

[0086] The sheet-like fiber substrate contained in the prepreg of this embodiment can be, for example, a known sheet-like fiber substrate used in various laminates for electrical insulating materials. Examples of the material for the sheet-like fiber substrate include inorganic fibers such as E-glass, D-glass, S-glass, and Q-glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof. These sheet-like fiber substrates have shapes such as woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat.

[0087] The prepreg of this embodiment can be produced, for example, by impregnating or applying the resin composition of this embodiment to a sheet-like fiber substrate, and then heating and drying the composition to B-stage. The temperature and time for heating and drying can be, for example, 50 to 200°C and 1 to 30 minutes, from the viewpoints of productivity and appropriately B-staging the resin composition of this embodiment.

[0088] The content of the resin composition in the prepreg of the present embodiment is preferably 20 to 90% by mass, more preferably 25 to 80% by mass, and even more preferably 30 to 75% by mass, from the viewpoint that better moldability can be easily obtained.

[0089] [Laminate] The laminate of the present embodiment is a laminate having a cured product of the resin composition of the present embodiment and a metal foil. Note that a laminate having a metal foil is sometimes called a metal-clad laminate.

[0090] Examples of metals for the metal foil include copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and alloys containing one or more of these metal elements.

[0091] The laminate of this embodiment can be produced, for example, by placing a metal foil on one or both sides of the prepreg of this embodiment and then subjecting it to a heat-pressure treatment. Typically, this heat-pressure treatment hardens the B-staged prepreg to obtain the laminate of this embodiment. When performing the heat-pressure treatment, only one prepreg may be used, or two or more prepregs may be laminated together. The heat-pressure treatment can be performed using, for example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like. The heat-pressure treatment can be performed under conditions of, for example, a temperature of 100 to 300°C, a time of 10 to 300 minutes, and a pressure of 1.5 to 5 MPa.

[0092] [Printed Wiring Board] The printed wiring board of this embodiment is a printed wiring board having a cured product of the resin composition of this embodiment. The printed wiring board of this embodiment can be produced, for example, by forming a conductor circuit on one or more materials selected from the group consisting of a cured product of the prepreg of this embodiment, a cured product of the resin film of this embodiment, and a laminate of this embodiment by a known method. Furthermore, if necessary, a multilayer printed wiring board can also be produced by further performing a multilayer adhesive process. The conductor circuit can be formed, for example, by appropriately performing a drilling process, a metal plating process, etching of a metal foil, or the like.

[0093] [Semiconductor Package] The semiconductor package of this embodiment is a semiconductor package including the printed wiring board of this embodiment and a semiconductor element. The semiconductor package of this embodiment can be manufactured, for example, by mounting the semiconductor element, memory, etc. on the printed wiring board of this embodiment by a known method.

[0094] The present embodiment will be specifically described below with reference to examples, although the present embodiment is not limited to the following examples.

[0095] In each example, the weight average molecular weight (Mw) was measured by the following method. It was calculated by gel permeation chromatography (GPC) from a calibration curve using standard polystyrene. The calibration curve was approximated by a cubic equation using standard polystyrene: TSKstandard POLYSTYRENE (Types: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, trade name]. The GPC measurement conditions are shown below. Apparatus: Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation] Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation] Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation] Column: Guard column; TSK Guard column HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR (all manufactured by Tosoh Corporation, trade names) Column size: 6.0 x 40 mm (guard column), 7.8 x 300 mm (column) Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL Injection volume: 20 μL Flow rate: 1.00 mL / min Measurement temperature: 40°C

[0096] Production Example 1: Production of Siloxane-Modified Maleimide Resin

[0043] 100 g of a diamine-modified siloxane having primary amino groups at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., product name: X-22-161A, amino group functional group equivalent: 800 g / mol), 450 g of 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, and 550 g of propylene glycol monomethyl ether were charged into a 2 L reactor equipped with a thermometer, a stirrer, and a reflux condenser and moisture meter, and the mixture was allowed to react at 120°C for 3 hours to produce a siloxane-modified maleimide compound-containing liquid. The weight-average molecular weight (Mw) of the resulting siloxane-modified maleimide compound was 2,500.

[0097] Examples 1 to 3, Comparative Examples 1 and 2 (Production of Resin Composition) Each component shown in Table 1 was blended in the amount shown in Table 1 (the blending amount shown in Table 1 is the mass part of the solid content), and mixed in methyl isobutyl ketone to obtain a resin composition with a solid content concentration of 50 mass%.

[0098] (Preparation of Prepreg) The resin composition prepared in each example was impregnated into glass cloth T2118 (trade name, manufactured by Nitto Boseki Co., Ltd.), and then heated at 120°C for 5 minutes to obtain a prepreg.

[0099] (Preparation of double-sided copper-clad laminate) A 12 μm thick electrolytic copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., product name "3EC-M3-VLP-12") was placed on both sides of the four prepregs so that the roughened surfaces faced the prepregs, and the laminate was heated and pressed at 240° C. for 80 minutes under vacuum pressing conditions of 3 MPa, to prepare a double-sided copper-clad laminate.

[0100] [Evaluation Method] Each evaluation was carried out according to the following methods. The results are shown in Table 1.

[0101] (Method for evaluating flame retardancy) In accordance with UL-94, the flaming burning time (seconds) was measured using five test specimens, and the average of the five was calculated as the average burning time. The test specimens were prepared by immersing a double-sided copper-clad laminate in a copper etching solution to remove the copper foil, and then cutting the laminate into a size of 125 mm x 13 mm.

[0102] (Method for measuring copper foil peel strength) The copper foil of each double-sided copper-clad laminate obtained in each example was partially etched to form a 3 mm wide copper foil line, which was used as a test piece. The copper foil peel strength was evaluated by measuring the load when the copper foil line was peeled off at a speed of 50 mm / min in a direction 90° to the adhesive surface. If the peeling load was 0.3 kN / m or more, it was determined that the copper foil adhesion was sufficient.

[0103] (Method for measuring glass transition temperature) The copper foil on both sides of the double-sided copper-clad laminate obtained in each example was removed by etching to prepare a 5 mm square test piece. Next, the test piece was attached to a thermomechanical measuring apparatus (TMA) (manufactured by TA Instruments Japan, product name "Q400") in a direction to detect displacement in the thickness direction of the laminate, and thermomechanical measurements were performed twice consecutively using a compression method under the following conditions: a measurement temperature range of 30 to 260 ° C, a load of 5 g, and a heating rate of 10 ° C / min. The glass transition temperature determined from the second thermomechanical measurement was used.

[0104] (Method for Evaluating Desmear Resistance) The double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to prepare a 40 mm × 40 mm test piece from which the copper foil had been removed. This test piece was treated with a swelling treatment solution "Swelling Dip Securigant P" (manufactured by Atotech Japan Co., Ltd.) at 70°C for 5 minutes. Next, after rinsing with water at room temperature for 2 minutes, the test piece was roughened by treatment with a roughening solution "Concentrate Compact CP" (manufactured by Atotech Japan Co., Ltd.) at 80°C for 10 or 15 minutes. Thereafter, the test piece was rinsed with water at 50°C for 2 minutes, neutralized with a neutralizing solution "Reduction Solution Securigant P500" (manufactured by Atotech Japan Co., Ltd.) at 40°C for 5 minutes, rinsed with water at room temperature for 5 minutes, and then dried. The desmear weight loss was calculated from the difference between the dry weight before desmearing and the dry weight after desmearing (dry weight before desmearing - dry weight after desmearing). The desmear weight loss in the double-sided copper-clad laminate of each example was converted into a percentage [100 × (desmear weight loss in each example) / (desmear weight loss in Comparative Example 1)] based on the desmear weight loss in the double-sided copper-clad laminate of Comparative Example 1, and this was shown as desmear resistance (%) in Table 1. For example, a desmear resistance of 100% in Example 1 means that there was no difference from the desmear resistance in Comparative Example 1.

[0105]

[0106] The details of each component shown in Table 1 are as follows: [Component (A)] Thermosetting resin 1: siloxane-modified maleimide resin prepared in Production Example 1 Thermosetting resin 2: "EPICLON (registered trademark) HP-9500", a naphthalene skeleton-containing epoxy resin (manufactured by DIC Corporation, trade name)

[0107] [Component (B)] Phosphate ester compound: 1,3-phenylenebis(di-2,6-xylenyl phosphate) (corresponding to the resin component)

[0108] [Component (C)] - Boehmite: manufactured by Kawai Lime Industry Co., Ltd., trade name "BMT-3LV", average particle diameter (D ５０ ) 1 to 5 μm

[0109] [Component (D)] Fused silica: spherical fused silica, average particle diameter (D ５０ ) 0.5 μm

[0110] [Component (E)] Curing accelerator: isocyanate masked imidazole, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "G-8009L"

[0111] It can be seen from Table 1 that the resin compositions of Examples 1 to 3 of this embodiment are excellent in flame retardancy while maintaining good copper foil adhesion, heat resistance, and desmear resistance.

Claims

1. A resin composition containing (A) a thermosetting resin, (B) a phosphorus-based flame retardant, and (C) boehmite.

2. The resin composition according to claim 1, wherein the content of (C) boehmite is 1 to 25 mass % of the total solid content (100 mass %) of the resin composition.

3. A resin composition according to claim 1 or 2, wherein the content of the (B) phosphorus-based flame retardant is 1 to 25 mass % of the total solid content (100 mass %) of the resin composition.

4. A resin composition according to claim 1 or 2, wherein the ratio of the content of the (C) boehmite to the content of the (B) phosphorus-based flame retardant [(C) / (B)] is 0.1 to 15.0 by mass.

5. The resin composition according to claim 1 or 2, wherein the phosphorus-based flame retardant (B) is a phosphoric acid ester compound.

6. The resin composition according to claim 1 or 2, wherein the thermosetting resin (A) contains at least one selected from the group consisting of maleimide resins and derivatives of the maleimide resins.

7. The resin composition according to claim 1 or 2, further comprising (D) an inorganic filler.

8. A prepreg containing the resin composition according to claim 1 or 2 or a semi-cured product of said resin composition.

9. A laminate comprising a cured product of the resin composition according to claim 1 or 2 and a metal foil.

10. A printed wiring board having a cured product of the resin composition according to claim 1 or 2.

11. A semiconductor package comprising the printed wiring board according to claim 10 and a semiconductor element.

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