JP7442255B2 - Resin composition for electronic materials - Google Patents

Description

The present invention relates to a resin composition for electronic materials.

In recent years, as the functionality and miniaturization of semiconductor packages widely used in electronic devices, communication equipment, personal computers, etc. have progressed, the degree of integration and high-density packaging of each component for semiconductor packages has accelerated in recent years. ing. Along with this, warpage of semiconductor plastic packages caused by the difference in thermal expansion coefficient between semiconductor elements and printed wiring boards for semiconductor plastic packages has become a problem, and various countermeasures have been taken.

One of the countermeasures is to reduce the thermal expansion of insulating layers used in printed wiring boards. This is a method of suppressing warpage by bringing the coefficient of thermal expansion of a printed wiring board close to that of a semiconductor element, and is currently being actively worked on (see, for example, Patent Documents 1 to 3).

JP2013-216884A Patent No. 3173332 JP2009-035728A

However, the reduction in thermal expansion of printed wiring boards by the conventional methods described in Patent Documents 1 to 3 has already reached its limit, and further reduction in thermal expansion is becoming difficult.

The present invention has been made in view of the above problems, and provides a resin composition for electronic materials that provides a cured product with a lower coefficient of thermal expansion and excellent electrical properties such as dielectric constant and dielectric loss tangent, and the electronic materials. The object of the present invention is to provide prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards using the resin compositions for use in the present invention.

The present inventors have made extensive studies to solve the above problems. As a result, the inventors discovered that the above problems could be solved by using a specific bismaleimide compound (A), and completed the present invention.

That is, the present invention is as follows.
[1]
Contains a bismaleimide compound (A) and a cyanate ester compound (C),
The bismaleimide compound (A) has two maleimide groups and one or more polyimide groups represented by the following formula (1),
The two maleimide groups are each independently bonded to both ends of the polyimide group through at least a first linking group in which 8 or more atoms are connected in a linear chain,
The content of the bismaleimide compound (A) is 5 to 100 parts by mass of the resin solid content.
60 parts by mass,
The content of the cyanate ester compound (C) is 1 with respect to 100 parts by mass of resin solid content.
0 to 60 parts by mass,
Resin composition for electronic materials.
[2]
The bismaleimide compound (A) further has one or more cyclic hydrocarbon groups that may contain a heteroatom having a ring with a number of atoms of 4 or more and 10 or less,
The two maleimide groups each independently represent the first group in which 8 or more atoms are connected in a linear chain.
bonded to the cyclic hydrocarbon group via a linking group,
The polyimide groups are each independently bonded to the cyclic hydrocarbon group via a second linking group in which 8 or more atoms are connected in a linear chain.
The resin composition for electronic materials according to [1].
[3]
the cyclic hydrocarbon group is an alicyclic group,
The resin composition for electronic materials according to [1] or [2].
[4]
[1] The linking group and/or the second linking group is a substituted or unsubstituted divalent hydrocarbon group,
The resin composition for electronic materials according to any one of [1] to [3].
[5]
The bismaleimide compound (A) has a repeating unit represented by the following formula (2),
The resin composition for electronic materials according to any one of [1] to [4].
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² is a substituted or unsubstituted hydrocarbon group in which the number of atoms constituting the ring is Represents a cyclic hydrocarbon group that may contain 4 or more and 10 or less heteroatoms.)
[6]
The bismaleimide compound (A) has a linear polymer structure represented by the following formula (3),
The resin composition for electronic materials according to any one of [1] to [5].
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² each independently represents a substituted or unsubstituted ring. Represents a cyclic hydrocarbon group that may contain a heteroatom having a number of constituent atoms of 4 or more and 10 or less, where n represents a number from 1 to 10.)
[7]
The weight average molecular weight of the bismaleimide compound (A) is 1×10 ³ to 1×10 ⁴ .
The resin composition for electronic materials according to any one of [1] to [6].
[8]
Maleimide compound (B) other than the bismaleimide compound (A), epoxy resin (D)
, a phenol resin (E), an oxetane resin (F), a benzoxazine compound (G), and a compound having a polymerizable unsaturated group (H).
The resin composition for electronic materials according to any one of [1] to [7].
[9]
The content of the epoxy resin (D) is 10 to 45 parts by mass based on 100 parts by mass of the resin solid content,
The resin composition for electronic materials according to [8] .
[10]
further comprising a filler (I);
The resin composition for electronic materials according to any one of [1] to [9] .
[11]
The content of the filler (I) is 50 to 300 parts by mass based on 100 parts by mass of the resin solid content,
The resin composition for electronic materials according to [10] .
[12]
base material and
and the resin composition for electronic materials according to any one of [1] to [11] , which is impregnated or applied to the base material.
prepreg.
[13]
sheet base material,
and the resin composition for electronic materials according to any one of [1] to [11] , which is laminated on one or both sides of the sheet base material.
Resin sheet.
[14]
an insulating layer;
a conductor layer laminated on one or both sides of the insulating layer,
The insulating layer contains the resin composition for electronic materials according to any one of [1] to [11] ,
Metal foil laminate.
[15]
comprising an insulating layer and a conductor layer formed on the surface of the insulating layer,
The insulating layer contains the resin composition for electronic materials according to any one of [1] to [11] ,
printed wiring board.

According to the present invention, there is provided a resin composition for electronic materials that provides a cured product with a lower coefficient of thermal expansion and excellent electrical properties such as dielectric constant and dielectric loss tangent, and a prepreg using the resin composition for electronic materials. Resin sheets, metal foil-clad laminates, and printed wiring boards can be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail, but the present invention is not limited thereto, and various modifications may be made without departing from the gist thereof. is possible.

[Resin composition for electronic materials]
The resin composition for electronic materials (hereinafter also simply referred to as "resin composition") of the present embodiment contains a bismaleimide compound (A), and the bismaleimide compound (A) has two maleimide groups and the following: one or more polyimide groups represented by formula (1), and each of the two maleimide groups independently connects at least a first linking group in which 8 or more atoms are connected in a linear chain. It is bonded to both ends of the polyimide group via the polyimide group.

[Bismaleimide compound (A)]
The bismaleimide compound (A) has two maleimide groups and one or more polyimide groups represented by the above formula (1), and each of the two maleimide groups independently has 8 or more polyimide groups. The polyimide group is bonded to both ends of the polyimide group at least through a first linking group in which atoms are linearly linked. The bismaleimide compound (A) having such a structure has an increased degree of freedom in the intramolecular position of maleimide groups and polyimide groups, and as a result, when made into a cured product, it has a high stress relaxation ability and a low coefficient of thermal expansion. A cured product is obtained. By using such a bismaleimide compound (A) with high stress relaxation ability, the stress difference between the resin and the base material (non-resin) becomes small, and the stress difference follows the physical properties of the base material, taking the prepreg described below as an example. The amount of thermal expansion is further reduced. Further, due to such a reduction in stress difference, it is possible to suppress the occurrence of warpage. Furthermore, due to the increased degree of freedom in the intramolecular positions of maleimide groups and polyimide groups, electrical properties such as dielectric constant and dielectric loss tangent of the cured product also tend to improve. Therefore, by using such a bismaleimide compound (A), a cured product having not only a high glass transition temperature (Tg) and heat resistance but also excellent electrical properties such as low thermal expansion, dielectric constant, and dielectric loss tangent can be obtained. It becomes possible to manufacture a resin composition for materials, as well as prepregs, resin sheets, metal foil-clad laminates, and printed wiring boards using the resin composition for electronic materials.

The first linking group is not particularly limited as long as 8 or more atoms are connected in a linear chain, but for example, it is a substituted or unsubstituted divalent hydrocarbon group having 8 or more carbon atoms. More preferably, it is a substituted or unsubstituted divalent hydrocarbon group having 8 to 10 carbon atoms. Substituted or unsubstituted divalent hydrocarbon groups are not particularly limited, but include, for example, substituted or unsubstituted linear aliphatic hydrocarbon groups, substituted or unsubstituted branched aliphatic hydrocarbon groups, and substituted or an unsubstituted cyclic aliphatic hydrocarbon group. Among these, substituted or unsubstituted linear aliphatic hydrocarbon groups are more preferred, and unsubstituted linear aliphatic hydrocarbon groups such as octylene group, nonamethylene group, decamethylene group, dodecamethylene group, hexadecamethylene group, octadecamethylene group, etc. An aliphatic hydrocarbon group is more preferred, and an octylene group, nonamethylene group, and decamethylene group are particularly preferred.

The two maleimide groups may each be independently bonded to both ends of the polyimide group via at least a first linking group in which 8 or more atoms are connected in a linear chain, and the first linking group Two maleimide groups may be bonded to both ends of the polyimide group via a group other than the first linking group. In particular, the bismaleimide compound (A) further has one or more cyclic hydrocarbon groups which may contain a heteroatom having a ring of 4 or more and 10 or less, and each of the two maleimide groups The polyimide group is independently bonded to the cyclic hydrocarbon group via the first linking group in which eight or more atoms are connected in a linear chain, and the polyimide group is independently bonded to the first linking group in which eight or more atoms are connected in a linear chain. It is preferable that the cyclic hydrocarbon group is bonded to the cyclic hydrocarbon group via a second linking group connected in a shape. In this way, the bismaleimide compound (A) having the second linking group tends to further increase the degree of freedom in the intramolecular position of the maleimide group and polyimide group. Further, by having the second linking group and the cyclic hydrocarbon group, the free volume increases, and as a result, the degree of freedom of the molecule tends to be further improved. Therefore, such bismaleimide compound (A) tends to have higher stress relaxation ability. Therefore, as mentioned above, by using such a bismaleimide compound (A), the thermal expansion coefficient of the resulting cured product tends to be lower, and the electrical properties such as dielectric constant and dielectric loss tangent tend to be better. be.

Here, the cyclic hydrocarbon group which may contain a heteroatom is not particularly limited as long as the number of atoms constituting the ring is 4 or more and 10 or less, but for example, a substituted or unsubstituted alicyclic group, a substituted or Examples include unsubstituted aromatic groups and substituted or unsubstituted heterocyclic groups. Among these, substituted or unsubstituted alicyclic groups, substituted or unsubstituted aromatic groups are preferred, substituted or unsubstituted alicyclic groups are more preferred, and alkyl group-substituted alicyclic groups are even more preferred. Note that the number of atoms constituting a ring is the number of atoms connected in a ring, and does not include the number of atoms such as substituents in side chains. By having such a cyclic hydrocarbon group, the bismaleimide compound (A) tends to have a higher stress relaxation ability, and as a result, the coefficient of thermal expansion of the obtained cured product tends to be lower, and the dielectric Electric properties such as dielectric constant and dielectric loss tangent tend to be better. Examples of the group of the alicyclic moiety in the substituted or unsubstituted alicyclic group include divalent or divalent or higher valent cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group. Further, the alkyl group in the alicyclic group substituted with an alkyl group is not particularly limited, but an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 3 to 10 carbon atoms is more preferable. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, Examples include neopentyl group, n-hexyl group, thexyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group, and n-decyl group. The number of alkyl groups in the alicyclic group substituted with an alkyl group may be one or two or more.

Further, the second linking group is not particularly limited as long as it has 8 or more atoms connected in a linear chain, but for example, it is a substituted or unsubstituted divalent hydrocarbon group having 8 or more carbon atoms. It is preferably a substituted or unsubstituted divalent hydrocarbon group having 8 to 10 carbon atoms. Substituted or unsubstituted divalent hydrocarbon groups are not particularly limited, but include, for example, substituted or unsubstituted linear aliphatic hydrocarbon groups, substituted or unsubstituted branched aliphatic hydrocarbon groups, and substituted or an unsubstituted cyclic aliphatic hydrocarbon group. Among these, substituted or unsubstituted linear aliphatic hydrocarbon groups are more preferred, and unsubstituted linear aliphatic hydrocarbon groups such as octylene group, nonamethylene group, decamethylene group, dodecamethylene group, hexadecamethylene group, octadecamethylene group, etc. An aliphatic hydrocarbon group is more preferred, and an octylene group, nonamethylene group, and decamethylene group are particularly preferred.

The bismaleimide compound (A) is preferably a compound having a repeating unit represented by the following formula (2). Such bismaleimide compounds (A) tend to have a higher stress relaxation ability, and as a result, the thermal expansion coefficient of the obtained cured product tends to be lower, and the electrical properties such as dielectric constant and dielectric loss tangent are lowered. It tends to be better.
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² is a substituted or unsubstituted hydrocarbon group in which the number of atoms constituting the ring is Represents a cyclic hydrocarbon group that may contain 4 or more and 10 or less heteroatoms.)

Here, R ² represents a cyclic hydrocarbon group that may include a heteroatom having a ring with a number of atoms of 4 or more and 10 or less, and R ³ represents a second linking group. Furthermore, R ¹ that is bonded to the cyclic hydrocarbon group R ² represents a first linking group when the other end is bonded to a maleimide group, and represents a second linking group when the other end is bonded to a polyimide group. represents. On the other hand, when the other end of R ¹ is bonded to, for example, a cyclic hydrocarbon group R ² , R ¹ may bond two cyclic hydrocarbon groups R ² . In addition, in formula (2), the hydrocarbon group in which 8 or more atoms are connected in a straight chain and the cyclic hydrocarbon group in which the number of atoms constituting the ring is 4 or more and 10 or less are the same as those mentioned above. I can do it.

More specifically, the bismaleimide compound (A) preferably has a linear polymer structure represented by the following formula (3). Such bismaleimide compounds (A) tend to have a higher stress relaxation ability, and as a result, the thermal expansion coefficient of the obtained cured product tends to be lower, and the electrical properties such as dielectric constant and dielectric loss tangent are lowered. It tends to be better.
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² each independently represents a substituted or unsubstituted ring. Represents a cyclic hydrocarbon group that may contain a heteroatom having a number of constituent atoms of 4 or more and 10 or less, where n represents a number from 1 to 10.)

In formula (3), R ¹ and R ³ are preferably octylene groups, and R ² is preferably a cycloalkylene group having an alkyl group having 6 to 8 carbon atoms as a substituent.

The bismaleimide compound (A) represented by the above formula (3) is not particularly limited, and for example, BMI-5000 (manufactured by Designer Molecules inc.) can be used. By using such a compound, the coefficient of thermal expansion tends to be further reduced.

The weight average molecular weight of the bismaleimide compound (A) is not particularly limited, but is preferably 1 x 10 ³ to 1 x 10 ⁴ , more preferably 2 x 10 ³ to 9 x 10 ³ , particularly preferably 3 ×10 ³ to 8×10 ³ . When the weight average molecular weight of the bismaleimide compound (A) is within the above range, the coefficient of thermal expansion of the resulting cured product tends to be further reduced. Note that the weight average molecular weight can be determined as a weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) analysis.

The content of the bismaleimide compound (A) is not particularly limited, but is preferably 5 to 60 parts by weight, preferably 10 to 55 parts by weight, and preferably 15 to 55 parts by weight, based on 100 parts by weight of the resin solid content. It is 50 parts by mass. When the content of the bismaleimide compound (A) is within the above range, the coefficient of thermal expansion, dielectric constant, dielectric loss tangent, and modulus of elasticity of the obtained cured product tend to be further reduced. In this embodiment, "resin solid content" refers to the components of the resin composition excluding solvents and fillers, unless otherwise specified, and "resin solid content of 100 parts by mass" refers to the resin composition. The total amount of components excluding the solvent and filler in the product is 100 parts by mass.

[Other ingredients]
In addition to the bismaleimide compound (A), the resin composition of the present embodiment may optionally contain a maleimide compound (B) other than the bismaleimide compound (A), a cyanate ester compound (C), and an epoxy resin. (D), a phenol resin (E), an oxetane resin (F), a benzoxazine compound (G), and a compound having a polymerizable unsaturated group (H). can. Among these, it is preferable to include a maleimide compound (B), a cyanate ester compound (C), and an epoxy resin (D). Each component will be explained below.

(Maleimide compound (B))
The maleimide compound (B) other than the bismaleimide compound (A) is not particularly limited, but the maleimide compound is not particularly limited as long as it has one or more maleimide groups in the molecule, such as N -Phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3,5-dimethyl-4-maleimidophenyl) ) methane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, maleimide compounds represented by formula (6), and these maleimide compounds. A prepolymer or a prepolymer of a maleimide compound and an amine compound may be mentioned. Among these, bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, and At least one selected from the group consisting of maleimide compounds represented by formula (6) is preferred. By including such a maleimide compound, the coefficient of thermal expansion of the obtained cured product tends to be further reduced and the heat resistance is further improved. The maleimide compounds may be used alone or in combination of two or more.
(In the formula, R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.)

The content of the maleimide compound (B) is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, and even more preferably 15 to 20 parts by weight, based on 100 parts by weight of the resin solid content. be. When the content of the maleimide compound (B) is within the above range, heat resistance and curability tend to be better.

(Cyanate ester compound (C))
The cyanate ester compound (C) is not particularly limited, but includes, for example, a naphthol aralkyl cyanate ester represented by formula (7), a novolac cyanate ester represented by formula (8), and a biphenylaralkyl cyanate ester. , bis(3,5-dimethyl4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanato Benzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, and Examples include 2,2'-bis(4-cyanatophenyl)propane; prepolymers of these cyanate esters, and the like. The cyanate ester compounds mentioned above may be used alone or in combination of two or more.
(In formula (7), R ⁶ each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Also, in formula (7), n ₂ represents an integer of 1 or more. n The upper limit of ₂ is usually 10, preferably 6.)
(In formula (8), R ⁷ each independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. Also, in formula (8), n ₃ represents an integer of 1 or more. n The upper limit of ₃ is usually 10, preferably 7.)

Among these, the cyanate ester compound (C) is a group consisting of a naphthol aralkyl cyanate ester represented by formula (7), a novolac type cyanate ester represented by formula (8), and a biphenylaralkyl cyanate ester. Preferably, it contains one or more selected from the group consisting of a naphthol aralkyl cyanate ester represented by formula (7) and a novolac type cyanate ester represented by formula (8). is more preferable. By using such a cyanate ester compound (C), a cured product with excellent flame retardancy, higher curability, and lower coefficient of thermal expansion tends to be obtained.

The content of the cyanate ester compound (C) is preferably 10 to 60 parts by weight, more preferably 10 to 55 parts by weight, and even more preferably 10 to 50 parts by weight based on 100 parts by weight of the resin solid content. Department. When the content of the cyanate ester compound (C) is within the above range, heat resistance, low dielectricity, low dielectric loss tangent, etc. tend to be better.

(Epoxy resin (D))
The epoxy resin (D) is not particularly limited, but examples include polyoxynaphthylene epoxy resin, bisphenol A epoxy resin, bisphenol E epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol A novolac. type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, xylene novolac type epoxy resin, polyfunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthalene skeleton modified novolac type epoxy resin, naphthylene ether type epoxy resin, phenol aralkyl type epoxy resin, anthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, triglycidyl isocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolak type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolac type epoxy resin, biphenylaralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol Examples include compounds obtained by epoxidizing double bonds such as type epoxy resins, phosphorus-containing epoxy resins, glycidylamine and butadiene, compounds obtained by reacting hydroxyl group-containing silicone resins with epichlorohydrin, and halogenated products thereof. These epoxy resins can be used alone or in combination of two or more. Among these, polyoxynaphthylene type epoxy resins are preferred. By including such an epoxy resin (D), the flame retardance and heat resistance of the obtained cured product tend to be further improved.

The content of the epoxy resin (D) is preferably 10 to 45 parts by weight, more preferably 10 to 40 parts by weight, and still more preferably 10 to 35 parts by weight, based on 100 parts by weight of the resin solid content. be. When the content of the epoxy resin (D) is within the above range, adhesiveness, flexibility, etc. tend to be better.

(phenol resin (E))
The phenol resin (E) is not particularly limited, but includes, for example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolac resin, bisphenol A novolac type phenol resin, Glycidyl ester type phenolic resin, aralkyl novolak type phenolic resin, biphenylaralkyl type phenolic resin, cresol novolac type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol novolak resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified novolak type phenolic resin, phenol aralkyl type phenol resin, naphthol aralkyl type phenol resin, dicyclopentadiene type phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, phosphorus-containing phenol resin, hydroxyl group-containing silicone resin, etc. Examples include, but are not particularly limited to. These phenolic resins can be used alone or in combination of two or more.

The content of the phenolic resin (E) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 35 parts by mass, based on 100 parts by mass of the resin solid content. be. When the content of the phenol resin (E) is within the above range, adhesiveness, flexibility, etc. tend to be better.

(Oxetane resin (F))
The oxetane resin (F) is not particularly limited, but includes, for example, oxetane, alkyloxetane such as 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3 -Methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluoroxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, OXT-101 (trade name manufactured by Toagosei Co., Ltd.) ), OXT-121 (trade name manufactured by Toagosei Co., Ltd.), and the like. These oxetane resins can be used alone or in combination of two or more.

The content of the oxetane resin (F) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 10 to 35 parts by mass, based on 100 parts by mass of the resin solid content. be. When the content of the oxetane resin (F) is within the above range, adhesiveness, flexibility, etc. tend to be better.

(Benzoxazine compound (G))
The benzoxazine compound (G) is not particularly limited, but includes, for example, bisphenol A type benzoxazine BA-BXZ (trade name manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (trade name manufactured by Konishi Chemical Co., Ltd.), bisphenol S type Examples include benzoxazine BS-BXZ (trade name, manufactured by Konishi Chemical). These benzoxazine compounds (G) can be used alone or in combination of two or more.

The content of the benzoxazine compound (G) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 10 to 35 parts by mass, based on 100 parts by mass of the resin solid content. It is. When the content of the benzoxazine compound (G) is within the above range, heat resistance etc. tend to be better.

(Compound (H) having a polymerizable unsaturated group)
The compound (H) having a polymerizable unsaturated group is not particularly limited, but includes, for example, vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, 2-hydroxyethyl (meth) ) acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa (meth)acrylates of monohydric or polyhydric alcohols such as (meth)acrylate; epoxy (meth)acrylates such as bisphenol A type epoxy (meth)acrylate and bisphenol F type epoxy (meth)acrylate; benzocyclobutene resin; Examples include (bis)maleimide resin. These compounds having a polymerizable unsaturated group can be used alone or in combination of two or more.

The content of the compound (H) having a polymerizable unsaturated group is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably is 10 to 35 parts by mass. When the content of the compound (H) having a polymerizable unsaturated group is within the above range, heat resistance, toughness, etc. tend to be better.

[Filler (I)]
The resin composition of this embodiment may further contain filler (I). As the filler (I), any known filler can be used as appropriate, and the type thereof is not particularly limited, and inorganic fillers and/or organic fillers commonly used in laminate applications are preferably used. I can do it.

Examples of inorganic fillers include, but are not limited to, silicas such as natural silica, fused silica, synthetic silica, amorphous silica, Aerosil, and hollow silica; silicon compounds such as white carbon; titanium white, zinc oxide, magnesium oxide, Metal oxides such as zirconium oxide; metal nitrides such as boron nitride, agglomerated boron nitride, silicon nitride, and aluminum nitride; metal sulfides such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heating aluminum hydroxide) metal hydrates such as boehmite and magnesium hydroxide; molybdenum compounds such as molybdenum oxide and zinc molybdate; zinc compounds such as zinc borate and zinc stannate; alumina , clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20 , short glass fibers (including fine glass powders such as E glass, T glass, D glass, S glass, and Q glass), hollow glass, and spherical glass. The inorganic fillers may be used alone or in combination of two or more. Among these, it is preferable to include boehmite and/or silica. By using such an inorganic filler, the coefficient of thermal expansion tends to be further reduced.

Examples of the organic filler include, but are not limited to, styrene-type, butadiene-type, acrylic-type rubber powder, core-shell type rubber powder, silicone resin powder, silicone rubber powder, silicone composite powder, and the like. These fillers can be used alone or in an appropriate combination of two or more.

The content of filler (I) is not particularly limited, but is preferably 50 to 300 parts by mass, more preferably 75 to 250 parts by mass, and even more preferably 100 parts by mass, based on 100 parts by mass of the resin solid content. ~200 parts by mass. When the content of filler (I) is within the above range, the coefficient of thermal expansion tends to be further reduced.

[Silane coupling agent and wetting and dispersing agent]
The resin composition of this embodiment may further contain a silane coupling agent and a wetting and dispersing agent. By including a silane coupling agent or a wetting and dispersing agent, the dispersibility of the filler and the adhesive strength between the resin component, the filler, and the substrate described below tend to be further improved.

The silane coupling agent is not particularly limited as long as it is a silane coupling agent that is generally used for surface treatment of inorganic materials, but examples include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ - Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylic silane compounds such as γ-acryloxypropyltrimethoxysilane; N-β-(N- Examples include cationic silane compounds such as vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds. The silane coupling agents may be used alone or in combination of two or more.

The wetting and dispersing agent is not particularly limited as long as it is a dispersion stabilizer used for paints, but for example, DISPER-110, 111, 118, 180, 161, BYK-W996 manufactured by Big Chemie Japan Co., Ltd. , W9010, W903, etc.

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. Examples of the curing accelerator include, but are not limited to, imidazoles such as triphenylimidazole; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, parachlorobenzoyl peroxide, di-tert-butyl-di-perphthalate, etc. organic peroxides; azo compounds such as azobisnitrile; N,N-dimethylbenzylamine, N,N-dimethylaniline, N,N-dimethyltoluidine, 2-N-ethylanilinoethanol, tri-n-butylamine , pyridine, quinoline, N-methylmorpholine, triethanolamine, triethylenediamine, tetramethylbutanediamine, N-methylpiperidine, and other tertiary amines; phenols, xylenol, cresol, resorcinol, catechol, and other phenols; naphthenic acid Organic metal salts such as lead, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetonate; Examples include those dissolved in compounds; inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; organic tin compounds such as dioctyltin oxide, other alkyltins, and alkyltin oxides; Among these, triphenylimidazole is particularly preferred because it accelerates the curing reaction and tends to have excellent glass transition temperature and coefficient of thermal expansion.

〔solvent〕
The resin composition of this embodiment may further contain a solvent. By including a solvent, the viscosity at the time of preparation of the resin composition is lowered, handling properties are further improved, and the impregnating property into a base material, which will be described later, tends to be further improved.

The solvent is not particularly limited as long as it can dissolve some or all of the resin components in the resin composition, but examples include ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatics such as toluene and xylene. Amides such as dimethylformamide; propylene glycol monomethyl ether and its acetate; and the like. The solvents may be used alone or in combination of two or more.

[Method for manufacturing resin composition]
The method for producing the resin composition of the present embodiment is not particularly limited, but includes, for example, a method in which each of the above-mentioned components is sequentially blended into a solvent and thoroughly stirred. At this time, in order to uniformly dissolve or disperse each component, known treatments such as stirring, mixing, and kneading treatments can be performed. Specifically, the dispersibility of the filler in the resin composition can be improved by performing the stirring and dispersion treatment using a stirring tank equipped with a stirrer having an appropriate stirring capacity. The above-mentioned stirring, mixing, and kneading treatments can be appropriately performed using, for example, a device for mixing such as a ball mill or a bead mill, or a known device such as a revolving or autorotating type mixing device.

Furthermore, when preparing the resin composition, an organic solvent can be used as necessary. The type of organic solvent is not particularly limited as long as it can dissolve the resin in the resin composition. Specific examples thereof are as described above.

[Application]
The above resin composition for electronic materials can be suitably used as a prepreg, a resin sheet, a metal foil-clad laminate, or a printed wiring board, and can be used more suitably for printed wiring board applications. The prepreg, resin sheet, metal foil-clad laminate, or printed wiring board will be explained below.

[Prepreg]
The prepreg of this embodiment includes a base material and the resin composition impregnated or applied to the base material. The prepreg manufacturing method can be carried out according to a conventional method and is not particularly limited. For example, after impregnating or coating a base material with the resin component in this embodiment, semi-curing (converting to B stage) by heating in a dryer at 100 to 200°C for 1 to 30 minutes, The prepreg of this embodiment can be produced.

The content of the resin composition (including filler (I)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and preferably 40 to 80% by mass, based on the total amount of prepreg. Mass%. When the content of the resin composition is within the above range, moldability tends to be further improved.

(Base material)
The base material is not particularly limited, and any known material used in various printed wiring board materials can be appropriately selected and used depending on the intended use and performance. Specific examples of fibers constituting the base material include, but are not particularly limited to, glass fibers such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, and T glass; Inorganic fibers other than glass; polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technora (registered trademark), Teijin Techno Products Ltd.) Fully aromatic polyamides such as 2,6-hydroxynaphthoic acid/parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), polyesters such as Zexion (registered trademark, manufactured by KB Seiren); polyparaphenylene Examples include organic fibers such as benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.) and polyimide. Among these, from the viewpoint of low coefficient of thermal expansion, at least one selected from the group consisting of E glass cloth, T glass cloth, S glass cloth, Q glass cloth, and organic fibers is preferable. These base materials may be used alone or in combination of two or more.

The shape of the base material is not particularly limited, and examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and surfacing mat. The method of weaving the woven fabric is not particularly limited, but for example, plain weaving, Nanako weaving, twill weaving, etc. are known, and the weaving method can be appropriately selected from these known methods depending on the intended use and performance. . Furthermore, glass woven fabrics subjected to fiber opening treatment or surface treated with a silane coupling agent or the like are preferably used. The thickness and mass of the base material are not particularly limited, but those having a thickness of about 0.01 to 0.3 mm are usually suitably used. In particular, from the viewpoint of strength and water absorption, the base material is preferably a woven glass fabric with a thickness of 200 μm or less and a mass of 250 g/m ² or less, and a glass woven fabric made of glass fibers of E glass, S glass, and T glass is preferable. More preferred.

[Resin sheet]
The resin sheet of this embodiment includes a sheet base material and the resin composition laminated on one or both sides of the sheet base material. A resin sheet is used as a means of thinning a sheet. For example, a thermosetting resin (inorganic filler) used for prepreg etc. is directly applied to a sheet base material (support) such as metal foil or film. ) can be manufactured by coating and drying.

The sheet base material is not particularly limited, but known materials used for various printed wiring board materials can be used. Examples include polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, polyethylene (PE) film, aluminum foil, copper foil, gold foil, and the like. Among these, electrolytic copper foil and PET film are preferred.

Examples of the coating method include a method in which a solution prepared by dissolving the resin composition of the present embodiment in a solvent is coated onto the sheet base material using a bar coater, die coater, doctor blade, baker applicator, or the like.

The resin sheet is preferably one in which the resin composition is applied to a sheet base material and then semi-cured (B-staged). Specifically, for example, after applying the above resin composition to a sheet base material such as copper foil, the resin sheet is semi-cured by heating in a dryer at 100 to 200°C for 1 to 60 minutes. Examples include manufacturing methods. The amount of the resin composition adhered to the sheet base material is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet.

Note that the resin sheet can also be used after being peeled off from the sheet base material.

[Metal foil clad laminate]
The metal foil clad laminate of this embodiment has an insulating layer and a conductor layer laminated on one or both sides of the insulating layer, and the insulating layer contains the resin composition. More specifically, prepreg or the above resin sheet can be used for the insulating layer. That is, the metal foil-clad laminate of this embodiment is obtained by laminating and curing at least one member selected from the group consisting of the prepreg and the resin sheet and a metal foil.

The insulating layer may be made of the above resin composition, one layer of prepreg, or a resin sheet, or may be formed by laminating two or more layers of the above resin composition, prepreg, or resin sheet.

The conductor layer can be a metal foil such as copper or aluminum. The metal foil used here is not particularly limited as long as it is used for printed wiring board materials, but known copper foils such as rolled copper foil and electrolytic copper foil are preferred. Further, the thickness of the conductor layer is not particularly limited, but is preferably 1 to 70 μm, more preferably 1.5 to 35 μm.

The method and conditions for forming the metal foil-clad laminate are not particularly limited, and methods and conditions for general printed wiring board laminates and multilayer boards can be applied. For example, when molding a metal foil-clad laminate, a multistage press machine, a multistage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. Further, in forming a metal foil-clad laminate, the temperature is generally 100 to 300°C, the pressure is 2 to 100 kgf/cm ² , and the heating time is generally 0.05 to 5 hours. Furthermore, if necessary, post-curing can be performed at a temperature of 150 to 300°C. Moreover, it is also possible to form a multilayer board by laminating and molding a combination of the above-mentioned prepreg and a separately prepared inner layer wiring board.

[Printed wiring board]
The printed wiring board of this embodiment is a printed wiring board including an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer contains the resin composition. The metal foil-clad laminate described above can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The metal foil-clad laminate described above has a low coefficient of thermal expansion, good formability, and chemical resistance, and can be particularly effectively used as a printed wiring board for semiconductor packages that requires such performance. I can do it.

Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, the above-mentioned metal foil-clad laminate (copper-clad laminate, etc.) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to create an inner layer substrate. The surface of the inner layer circuit of this inner layer board is subjected to surface treatment to increase adhesive strength as required, and then the required number of sheets of prepreg described above are layered on the surface of the inner layer circuit, and then metal foil for the outer layer circuit is laminated on the outside. Then heat and press to form an integral mold. In this way, a multilayer laminate is produced in which an insulating layer made of a base material and a cured product of a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after drilling holes for through holes and via holes in this multilayer laminate, a desmear process is performed to remove smear, which is resin residue derived from the resin components contained in the cured material layer. . After that, a plating metal film is formed on the wall of this hole to conduct the inner layer circuit and the metal foil for the outer layer circuit, and then the metal foil for the outer layer circuit is etched to form the outer layer circuit, and the printed wiring board is manufactured. be done.

For example, the above-mentioned prepreg (base material and the above-mentioned resin composition attached thereto), the resin composition layer (layer consisting of the above-mentioned resin composition) of the metal foil-clad laminate contains the above-mentioned resin composition. This will constitute an insulating layer.

Furthermore, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductive layer to form a circuit on the prepreg, the resin sheet, and the resin composition. At this time, an electroless plating method can also be used to form the conductor layer.

The printed wiring board of this embodiment is suitable for use in semiconductor packages because the above-mentioned insulating layer maintains an excellent elastic modulus even under reflow temperatures during semiconductor mounting, thereby effectively suppressing warping of semiconductor plastic packages. It can be used particularly effectively as a printed wiring board.

Hereinafter, the present invention will be explained in more detail using Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Synthesis example 1]
In the reactor, an α-naphthol aralkyl type phenol resin (SN495V, OH group equivalent: 236 g/eq., manufactured by Nippon Steel Chemical Co., Ltd.) is used.The number of repeating units n of naphthol aralkyl is 1 to 5. ) was dissolved in 500 mL of chloroform, and 0.7 mol of triethylamine was added to this solution. While maintaining the temperature at -10° C., 300 g of a chloroform solution of 0.93 mol of cyanogen chloride was added dropwise into the reactor over 1.5 hours, and after the addition was completed, the mixture was stirred for 30 minutes. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was added dropwise into the reactor and stirred for 30 minutes to complete the reaction. After the by-produced triethylamine hydrochloride was filtered out from the reaction solution, the resulting filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water, which was repeated four times. After drying this with sodium sulfate, it was evaporated at 75°C and further degassed under reduced pressure at 90°C to obtain a brown solid α-naphthol aralkyl cyanate ester resin (SNCN). When the obtained α-naphthol aralkyl cyanate ester resin was analyzed by infrared absorption spectrum, absorption of cyanate ester groups around 2264 cm ⁻¹ was confirmed.

[Example 1]
17.3 parts by mass of a novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 28.7 parts by mass of the naphthol aralkyl-type cyanate ester resin obtained in Synthesis Example 1, and a polyoxynaphthylene-type 29.4 parts by mass of epoxy resin (HP-6000, manufactured by DIC Corporation), 24.6 parts by mass of bismaleimide compound (BMI-5000, manufactured by Designer Molecules inc.), silica (SC-5050MOB, average particle diameter) A varnish was obtained by mixing 120 parts by mass of 1.5 μm (manufactured by Admatex Co., Ltd.) and 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.). This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick T glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg with a resin content of 44.5% by mass. A metal foil-clad laminate was produced using the obtained prepreg, and the thermal expansion coefficient was measured by the TMA tensile method described below. Table 1 shows the results.

In the bismaleimide compound (BMI-5000), in formula (3), R ¹ and R ³ are octyl groups, R ² is a cyclohexyl group having a hexyl group and an octyl group as substituents, and the weight is This is a compound with an average molecular weight of 5,000.

[Comparative example 1]
24.6 parts by mass of a novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 36.8 parts by mass of the naphthol aralkyl-type cyanate ester resin obtained in Synthesis Example 1, and a polyoxynaphthylene type. 38.6 parts by mass of epoxy resin (HP-6000, manufactured by DIC Corporation), 120 parts by mass of silica (SC-5050MOB, average particle diameter 1.5 μm, manufactured by Admatex Corporation), 2,4,5 -0.5 parts by mass of triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick T glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg with a resin content of 44.5% by mass. A metal foil-clad laminate was produced using the obtained prepreg, and the thermal expansion coefficient was measured using the TMA tensile method described below. Table 1 shows the results.

[Comparative example 2]
12.7 parts by mass of a novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 30.9 parts by mass of the naphthol aralkyl-type cyanate ester resin obtained in Synthesis Example 1, and a polyoxynaphthylene type. 31.8 parts by mass of epoxy resin (HP-6000, manufactured by DIC Corporation), 24.6 parts by mass of a bismaleimide compound represented by the following formula (BMI-1000P, manufactured by Daiwa Chemical Industries, Ltd.), silica Mix 120 parts by mass of (SC-5050MOB, average particle size 1.5 μm, manufactured by Admatex Co., Ltd.) and 0.5 parts by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and got varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick T glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg with a resin content of 44.5% by mass. A metal foil-clad laminate was produced using the obtained prepreg, and the thermal expansion coefficient was measured using the TMA tensile method described below. Table 1 shows the results.
(In the formula, the average value of n is 14.)

[Production of metal foil clad laminate]
Eight prepregs obtained in Example 1, Comparative Example 1, or Comparative Example 2 were stacked, 12 μm thick electrolytic copper foil (3EC-III, manufactured by Mitsui Mining & Mining Co., Ltd.) was placed above and below, and a pressure of 30 kgf/ cm ² and a temperature of 220° C. for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.8 mm.

[Thermal expansion coefficient (TMA tensile method)]
The longitudinal thermal expansion coefficient of the glass cloth was measured for the insulating layer of the laminate using the TMA method (thermo-mechanical analysis) specified in JlS C 6481 for the obtained 8-ply metal foil-clad laminate. I calculated that value. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, measurements were performed using a thermomechanical analyzer (manufactured by TA Instruments) using the TMA tensile method. In the TMA tensile method, the load was 2.5 g, the chuck distance was 10 mm, the temperature was raised from 40°C to 340°C at a rate of 10°C per minute, and the linear thermal expansion coefficient (ppm/°C) from 60°C to 120°C was measured.

[Example 2]
50 parts by mass of the naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, 50 parts by mass of a bismaleimide compound (BMI-3000J, manufactured by Designer Molecules inc.), and silica (SC-5050MOB, average particle diameter 1.5 μm). , manufactured by Admatex Co., Ltd.) and 0.05 parts by mass of zinc octylate (manufactured by Nihon Kagaku Sangyo Co., Ltd.) to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated and coated on a 0.1 mm thick T glass woven fabric, and dried by heating at 140° C. for 3 minutes to obtain a prepreg with a resin content of 50% by mass. A metal foil-clad laminate was produced using the obtained prepreg, and the physical properties were evaluated using the method described below. The results are shown in Table 2. Note that the thermal expansion coefficient was measured by the TMA compression method.

The bismaleimide compound (BMI-3000J) has formula (3) in which R ¹ and R ³ are octyl groups, R ² is a cyclohexyl group having a hexyl group and an octyl group as substituents, and the weight is This is a compound with an average molecular weight of 3000.

[Comparative example 3]
In place of the bismaleimide compound (BMI-3000J), 50 parts by mass of a novolak-type maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used, and the amount of zinc octylate used was 0.1 part by mass. Except for this, a prepreg with a resin content of 50% by mass was obtained in the same manner as in Example 2. A metal foil-clad laminate was produced using the obtained prepreg, and the physical properties were evaluated using the method described below. The results are shown in Table 2. Note that the thermal expansion coefficient was measured by the TMA compression method.

[Production of metal foil clad laminate]
Eight sheets of the prepreg obtained in Example 2 or Comparative Example 3 were stacked, and 12 μm thick electrolytic copper foil (3EC-M3-VLP, manufactured by Mitsui Kinzoku Co., Ltd.) was placed above and below, and a pressure of 30 kgf/cm ² was applied. Lamination molding was performed at a temperature of 220° C. for 120 minutes to obtain a metal foil-clad laminate with an insulating layer thickness of 0.8 mm.

〔Glass-transition temperature〕
The glass transition temperature of the obtained 8-ply metal foil-clad laminate was measured by the DMA method using a dynamic viscoelastic analyzer (manufactured by TA Instruments) in accordance with JIS C6481.

[Thermal expansion coefficient (TMA compression method)]
The longitudinal thermal expansion coefficient of the glass cloth was measured for the insulating layer of the laminate using the TMA method (thermo-mechanical analysis) specified in JlS C 6481 for the obtained 8-ply metal foil-clad laminate. I calculated that value. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, measurements were performed using a thermomechanical analyzer (manufactured by TA Instruments) using the TMA compression method. In the TMA compression method, the temperature was raised at 10°C per minute from 40°C to 340°C under a load of 5 g, and the linear thermal expansion coefficient (ppm/°C) from 60°C to 120°C was measured.

[Laminated plate permittivity]
Using a test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the dielectric constant was measured three times at 2 and 10 GHz using the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). The average value was calculated.

[Laminated plate dielectric loss tangent]
Using a test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the dielectric loss tangent at 2 and 10 GHz was measured three times using the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies). The average value was calculated.

[Thermogravimetric reduction rate]
After removing the copper foil of the obtained metal foil-clad laminate with an insulating layer thickness of 0.8 mm by etching, a simultaneous differential thermogravimetric measurement device TG/DTA6200 (SI - Thermogravimetric reduction when the temperature reaches 450°C when the test piece is 3mm x 3mm x 0.8mm and heated at a starting temperature of 300°C and a heating rate of 10°C/min using a test piece (manufactured by Nano Technology Co., Ltd.) under nitrogen flow. The rate (thermal decomposition amount (%)) and the temperature at which the thermal weight reduction rate was 1% were determined based on the following formula.
Thermogravimetric reduction rate (%) = (I-J)/I x 100
(I represents the weight at the starting temperature, J represents the weight at 450°C.)

The resin composition for electronic materials of the present invention has industrial applicability as a material for prepregs, resin sheets, metal foil-clad laminates, or printed wiring boards.

Claims (13)

Contains a bismaleimide compound (A), a cyanate ester compound (C) and an epoxy resin (D) ,
The bismaleimide compound (A) has two maleimide groups and one or more polyimide groups represented by the following formula (1),
The two maleimide groups are each independently bonded to both ends of the polyimide group through at least a first linking group in which 8 or more atoms are connected in a linear chain,
The content of the bismaleimide compound (A) is 5 to 60 parts by mass based on 100 parts by mass of resin solid content,
The content of the cyanate ester compound (C) is 10 to 60 parts by mass based on 100 parts by mass of resin solid content,
The content of the epoxy resin (D) is 10 to 45 parts by mass based on 100 parts by mass of resin solid content,
The bismaleimide compound (A) further has two or more cyclic hydrocarbon groups that may contain a heteroatom having a ring with a number of atoms of 4 or more and 10 or less,
The two maleimide groups are each independently bonded to the cyclic hydrocarbon group via the first linking group in which 8 or more atoms are connected in a linear chain,
The polyimide groups are each independently bonded to the cyclic hydrocarbon group via a second linking group in which 8 or more atoms are connected in a linear chain.
Resin composition for electronic materials.
the cyclic hydrocarbon group is an alicyclic group,
The resin composition for electronic materials according to claim 1. The first connecting group and/or the second connecting group is a substituted or unsubstituted divalent hydrocarbon group,
The resin composition for electronic materials according to claim 1 or 2. The bismaleimide compound (A) has a repeating unit represented by the following formula (2),
The resin composition for electronic materials according to any one of claims 1 to 3.
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² is a substituted or unsubstituted hydrocarbon group in which the number of atoms constituting the ring is Represents a cyclic hydrocarbon group that may contain 4 or more and 10 or less heteroatoms.) The bismaleimide compound (A) has a linear polymer structure represented by the following formula (3),
The resin composition for electronic materials according to any one of claims 1 to 4.
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are connected in a linear chain, and R ² each independently represents a substituted or unsubstituted ring. Represents a cyclic hydrocarbon group that may contain a heteroatom having a number of constituent atoms of 4 or more and 10 or less, where n represents a number from 1 to 10.) The weight average molecular weight of the bismaleimide compound (A) is 1×10 ³ to 1×10 ⁴ .
The resin composition for electronic materials according to any one of claims 1 to 5. A group consisting of a maleimide compound (B) other than the bismaleimide compound (A) , a phenol resin (E), an oxetane resin (F), a benzoxazine compound (G), and a compound (H) having a polymerizable unsaturated group. further including one or more selected from
The resin composition for electronic materials according to any one of claims 1 to 6. further comprising a filler (I);
The resin composition for electronic materials according to any one of claims 1 to 7 . The content of the filler (I) is 50 to 300 parts by mass based on 100 parts by mass of the resin solid content,
The resin composition for electronic materials according to claim 8 . base material and
and the resin composition for electronic materials according to any one of claims 1 to 9 , which is impregnated or applied to the base material.
prepreg. sheet base material,
and the resin composition for electronic materials according to any one of claims 1 to 9 , which is laminated on one or both sides of the sheet base material.
Resin sheet. an insulating layer;
a conductor layer laminated on one or both sides of the insulating layer,
The insulating layer contains the resin composition for electronic materials according to any one of claims 1 to 9 .
Metal foil laminate. comprising an insulating layer and a conductor layer formed on the surface of the insulating layer,
The insulating layer contains the resin composition for electronic materials according to any one of claims 1 to 9 .
printed wiring board.