JP2018090728A - Resin composition for electronic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a resin composition for an electronic material for providing a cured product having a lower coefficient of thermal expansion and excellent electrical characteristics such as dielectric constant and dielectric loss tangent; and a prepreg, a resin sheet, a metal foil-clad laminate and a printed wiring board using the resin composition for an electronic material.SOLUTION: There is provided a resin composition for an electronic material which comprises a bismaleimide compound (A), wherein the bismaleimide compound (A) has two maleimide groups and a polyimide group represented by the following formula (1), the two maleimide groups each independently are bonded to both terminals of the polyimide group at least through a first linking group to which 8 or more atoms are linearly linked.SELECTED DRAWING: None

Description

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

  In recent years, as semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more sophisticated and smaller in size, higher integration and higher density mounting of each component for semiconductor packages has been accelerated in recent years. ing. Accordingly, warping of the semiconductor plastic package caused by the difference in thermal expansion coefficient between the semiconductor element and the printed wiring board for the semiconductor plastic package has become a problem, and various countermeasures have been taken.

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

JP 2013-216684 A Japanese Patent No. 3173332 JP 2009-035728 A

  However, the low thermal expansion of the printed wiring board by the conventional methods described in Patent Documents 1 to 3 is already approaching its limit, and it is difficult to further reduce the thermal expansion.

  The present invention has been made in view of the above problems, and a resin composition for an electronic material that gives a cured product having a lower coefficient of thermal expansion and excellent electrical characteristics such as dielectric constant and dielectric loss tangent, and the electronic material An object of the present invention is to provide a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board using the resin composition.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the above-mentioned problems can be solved by using the predetermined bismaleimide compound (A), and the present invention has been completed.

That is, the present invention is as follows.
[1]
A bismaleimide compound (A),
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 linearly connected.
Resin composition for electronic materials.
[2]
The bismaleimide compound (A) further has one or more cyclic hydrocarbon groups that may contain a hetero atom having 4 to 10 atoms constituting the ring,
Each of the two maleimide groups is independently bonded to the cyclic hydrocarbon group via the first linking group in which 8 or more atoms are linearly linked;
Each of the polyimide groups is independently bonded to the cyclic hydrocarbon group via a second linking group in which 8 or more atoms are connected in a straight chain.
[1] The resin composition for electronic materials according to [1].
[3]
The cyclic hydrocarbon group is an alicyclic group;
The resin composition for electronic materials as described in [1] or [2].
[4]
The linking group of [1] and / or the second linking group is a substituted or unsubstituted divalent hydrocarbon group.
[1]-The resin composition for electronic materials as described in any one of [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 linked in a straight chain, and R ² represents the number of atoms constituting the ring, which is substituted or unsubstituted. Represents a cyclic hydrocarbon group which 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].
(Wherein R ¹ and R ³ each independently represents a hydrocarbon group in which 8 or more atoms are linearly linked, and R ² each independently represents a substituted or unsubstituted ring. The cyclic hydrocarbon group which may contain a hetero atom having 4 to 10 atoms is included, and n represents a number of 1 to 10.
[7]
The bismaleimide compound (A) has a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ .
The resin composition for electronic materials as described in any one of [1] to [6].
[8]
Maleimide compound (B) other than the bismaleimide compound (A), cyanate ester compound (C), epoxy resin (D), phenol resin (E), oxetane resin (F), benzoxazine compound (G), and polymerization Further including one or more selected from the group consisting of compounds (H) having a possible unsaturated group,
The resin composition for electronic materials according to any one of [1] to [7].
[9]
Content of the said bismaleimide compound (A) is 5-60 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials according to any one of [1] to [8].
[10]
Content of the said cyanate ester compound (C) is 10-60 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials as described in [8] or [9].
[11]
Content of the said epoxy resin (D) is 10-45 mass parts with respect to 100 mass parts of resin solid content,
[8] The resin composition for electronic materials as described in any one of [10].
[12]
Further comprising a filler (I),
The resin composition for electronic materials according to any one of [1] to [11].
[13]
Content of the said filler (I) is 50-300 mass parts with respect to 100 mass parts of resin solid content,
[12] The resin composition for electronic materials according to [12].
[14]
A substrate;
The resin composition for electronic materials according to any one of [1] to [13], impregnated or coated on the base material,
Prepreg.
[15]
A sheet substrate;
The resin composition for electronic materials according to any one of [1] to [13], which is laminated on one side or both sides of the sheet base material,
Resin sheet.
[16]
An insulating layer;
A conductive layer laminated on one or both sides of the insulating layer,
The insulating layer includes the resin composition for electronic materials according to any one of [1] to [13].
Metal foil-clad laminate.
[17]
Having an insulating layer and a conductor layer formed on the surface of the insulating layer;
The insulating layer includes the resin composition for electronic materials according to any one of [1] to [13].
Printed wiring board.

  According to the present invention, a resin composition for electronic materials that gives a cured product having 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, A resin sheet, a metal foil-clad laminate, and a printed wiring board can be provided.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Resin composition for electronic materials]
The resin composition for electronic materials of the present embodiment (hereinafter also simply referred to as “resin composition”) includes a bismaleimide compound (A), and the bismaleimide compound (A) includes two maleimide groups and Each having two or more polyimide groups represented by the formula (1), and each of the two maleimide groups independently includes at least a first linking group in which 8 or more atoms are linked in a straight chain. And bonded to both ends of 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 is independently 8 or more. The atoms are bonded to both ends of the polyimide group through at least a first linking group in which atoms are linearly connected. The bismaleimide compound (A) having such a structure has an increased degree of freedom in the intramolecular positions of the maleimide group and the polyimide group, and as a result, has a high stress relaxation ability when made into a cured product and a low coefficient of thermal expansion. A cured product is obtained. By using the bismaleimide compound (A) having such a high stress relaxation capability, if the prepreg described later is taken as an example, the stress difference between the resin and the base material (non-resin) is reduced, and the physical properties of the base material are followed. The amount of thermal expansion is further reduced. In addition, the occurrence of warpage can be suppressed by reducing the stress difference. Furthermore, electrical characteristics such as dielectric constant and dielectric loss tangent in the cured product tend to be further improved due to an increase in the degree of freedom of the intramolecular positions of the maleimide group and the polyimide group. Therefore, by using such a bismaleimide compound (A), an electron that gives a cured product that is excellent not only in high glass transition temperature (Tg) and heat resistance but also in electrical characteristics such as low thermal expansion, dielectric constant and dielectric loss tangent. The resin composition for materials, and the prepreg, resin sheet, metal foil-clad laminate, and printed wiring board using the resin composition for electronic materials can be produced.

  The first linking group is not particularly limited as long as 8 or more atoms are linked in a straight chain. For example, the first linking group 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. Although it does not specifically limit as a substituted or unsubstituted bivalent hydrocarbon group, For example, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, and substituted Or an unsubstituted cycloaliphatic hydrocarbon group is mentioned. Of these, a substituted or unsubstituted linear aliphatic hydrocarbon group is more preferable, and an unsubstituted linear chain such as an octylene group, a nonamethylene group, a decamethylene group, a dodecamethylene group, a hexadecamethylene group, an octadecamethylene group, and the like. An aliphatic hydrocarbon group is more preferable, and an octylene group, a nonamethylene group, and a decamethylene group are particularly preferable.

  The two maleimide groups may be independently bonded to both ends of the polyimide group via at least a first linking group in which 8 or more atoms are linearly linked. Two maleimide groups may be bonded to both ends of the polyimide group via a group other than the first linking group. Among them, the bismaleimide compound (A) further has one or more cyclic hydrocarbon groups which may contain a hetero atom having 4 to 10 atoms constituting the ring, and the two maleimide groups are each Independently, the polyimide group is bonded to the cyclic hydrocarbon group via the first linking group in which 8 or more atoms are linearly connected, and each of the polyimide groups is independently 8 or more atoms in a straight line. It is preferable that it is what is couple | bonded with the said cyclic hydrocarbon group through the 2nd coupling group connected in the shape. Thus, the bismaleimide compound (A) having the second linking group tends to further increase the degree of freedom in the intramolecular positions of the maleimide group and the 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 molecular freedom tends to be further improved. Therefore, such a bismaleimide compound (A) tends to have higher stress relaxation ability. Therefore, by using such a bismaleimide compound (A), as described above, the thermal expansion coefficient of the obtained cured product tends to be further reduced, and electric characteristics such as dielectric constant and dielectric loss tangent tend to be more excellent. is there.

  Here, the cyclic hydrocarbon group which may contain a hetero atom is not particularly limited as long as the number of atoms constituting the ring is 4 or more and 10 or less. For example, a substituted or unsubstituted alicyclic group, substituted or substituted Examples thereof include an unsubstituted aromatic group and a substituted or unsubstituted heterocyclic group. Among these, a substituted or unsubstituted alicyclic group and a substituted or unsubstituted aromatic group are preferable, a substituted or unsubstituted alicyclic group is more preferable, and an alkyl group-substituted alicyclic group is more preferable. The number of atoms constituting the ring is the number of atoms linked in a ring, and does not include the number of atoms such as side chain substituents. By having such a cyclic hydrocarbon group, the bismaleimide compound (A) tends to have higher stress relaxation capability, and as a result, the thermal expansion coefficient of the resulting cured product tends to be further lowered, and the dielectric Electric characteristics such as rate and dielectric loss tangent tend to be more excellent. Examples of the alicyclic moiety in the substituted or unsubstituted alicyclic group include a divalent or divalent or higher valent cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclodecyl group. Moreover, 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 a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, A neopentyl group, n-hexyl group, texyl group, n-heptyl group, n-octyl group, n-ethylhexyl group, n-nonyl group and n-decyl group can be mentioned. The alkyl group-substituted alicyclic group may have one alkyl group or two or more alkyl groups.

  The second linking group is not particularly limited as long as 8 or more atoms are linked in a straight chain. For example, 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. Although it does not specifically limit as a substituted or unsubstituted bivalent hydrocarbon group, For example, a substituted or unsubstituted linear aliphatic hydrocarbon group, a substituted or unsubstituted branched aliphatic hydrocarbon group, and substituted Or an unsubstituted cycloaliphatic hydrocarbon group is mentioned. Of these, a substituted or unsubstituted linear aliphatic hydrocarbon group is more preferable, and an unsubstituted linear chain such as an octylene group, a nonamethylene group, a decamethylene group, a dodecamethylene group, a hexadecamethylene group, an octadecamethylene group, and the like. An aliphatic hydrocarbon group is more preferable, and an octylene group, a nonamethylene group, and a decamethylene group are particularly preferable.

The bismaleimide compound (A) is preferably a compound having a repeating unit represented by the following formula (2). Such a bismaleimide compound (A) tends to have a higher stress relaxation capability, and as a result, the thermal expansion coefficient of the resulting cured product tends to be lower, and electrical properties such as dielectric constant and dielectric loss tangent are low. 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 linked in a straight chain, and R ² represents the number of atoms constituting the ring, which is substituted or unsubstituted. Represents a cyclic hydrocarbon group which may contain 4 or more and 10 or less heteroatoms.)

Here, R ² represents a cyclic hydrocarbon group that may contain a hetero atom having 4 to 10 atoms constituting the ring, and R ³ represents a second linking group. R ¹ bonded to the cyclic hydrocarbon group R ² represents the first linking group when the other end is bonded to the maleimide group, and the second linking group when the other end is bonded to the 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 be a bond of ^two cyclic hydrocarbon groups R ² . In the formula (2), the hydrocarbon group in which 8 or more atoms are connected in a straight chain and the cyclic hydrocarbon group having 4 to 10 atoms constituting the ring are exemplified as those described above. Can do.

More specifically, the bismaleimide compound (A) preferably has a linear polymer structure represented by the following formula (3). Such a bismaleimide compound (A) tends to have a higher stress relaxation capability, and as a result, the thermal expansion coefficient of the resulting cured product tends to be lower, and electrical properties such as dielectric constant and dielectric loss tangent are low. It tends to be better.
(Wherein R ¹ and R ³ each independently represents a hydrocarbon group in which 8 or more atoms are linearly linked, and R ² each independently represents a substituted or unsubstituted ring. The cyclic hydrocarbon group which may contain a hetero atom having 4 to 10 atoms is included, and n represents a number of 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. For example, BMI-5000 (manufactured by Designer Moleculars Inc.) can be used. By using such a compound, the thermal expansion coefficient tends to be further reduced.

The weight average molecular weight of the bismaleimide compound (A) is not particularly limited, but is preferably 1 × 10 ³ to 1 × 10 ⁴ , more preferably 2 × 10 ^{3 to} 9 × 10 ³ , and 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 thermal expansion coefficient of the obtained cured product tends to be further reduced. In addition, a weight average molecular weight can be calculated | required as a weight average molecular weight (Mw) of polystyrene conversion by gel permeation chromatography (GPC) analysis.

  Although content of a bismaleimide compound (A) is not specifically limited, Preferably it is 5-60 mass parts with respect to 100 mass parts of resin solid content, Preferably it is 10-55 mass parts, Preferably 15- 50 parts by mass. When the content of the bismaleimide compound (A) is within the above range, the thermal expansion coefficient, dielectric constant, dielectric loss tangent, and elastic modulus of the obtained cured product tend to be further reduced. In the present embodiment, “resin solid content” means a component in the resin composition excluding a solvent and a filler unless otherwise specified, and “resin solid content 100 parts by mass” means a resin composition. The sum of the 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 includes a maleimide compound (B) other than the bismaleimide compound (A), a cyanate ester compound (C), and an epoxy resin as necessary. It may further include one or more selected from the group consisting of (D), phenol resin (E), oxetane resin (F), benzoxazine compound (G), and compound (H) having a polymerizable unsaturated group. it can. Among these, it is preferable that a maleimide compound (B), a cyanate ester compound (C), and an epoxy resin (D) are included. Hereinafter, each component will be described.

(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 is a compound having one or more maleimide groups in the molecule. -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, a maleimide compound represented by formula (6), of these maleimide compounds Examples include prepolymers, or prepolymers of maleimide compounds and amine compounds. That. 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 thermal expansion coefficient of the obtained cured product is further reduced, and the heat resistance tends to be further improved. Maleimide compounds may be used alone or in combination of two or more.
(In the formula, each R ₅ 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 mass, more preferably 10 to 25 parts by mass, and further preferably 15 to 20 parts by mass with respect to 100 parts by mass of the resin solid content. is there. When the content of the maleimide compound (B) is within the above range, the heat resistance and curability tend to be more excellent.

(Cyanate ester compound (C))
Although it does not specifically limit as cyanate ester compound (C), For example, the naphthol aralkyl type cyanate ester shown by Formula (7), the novolak type cyanate ester and biphenyl aralkyl type cyanate ester shown by Formula (8) Bis (3,5-dimethyl-4-cyanatophenyl) methane, bis (4-cyanatophenyl) methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanate 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) And ether, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) sulfone, and 2,2′-bis (4-cyanatophenyl) propane; prepolymers of these cyanate esters. You may use the cyanate ester compound mentioned above individually by 1 type or in combination of 2 or more types.
(In formula (7), each R ⁶ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In formula (7), n ₂ represents an integer of 1 or more. N The upper limit of ₂ is usually 10 and preferably 6)
(In formula (8), each R ⁷ independently represents a hydrogen atom or a methyl group, and among these, a hydrogen atom is preferable. In formula (8), n ₃ represents an integer of 1 or more. N The upper limit of ₃ is usually 10 and preferably 7)

  Among these, the cyanate ester compound (C) is a group consisting of a naphthol aralkyl cyanate ester represented by the formula (7), a novolak cyanate ester represented by the formula (8), and a biphenyl aralkyl cyanate ester. It is preferable to include at least one selected from the group consisting of naphthol aralkyl cyanate represented by the formula (7) and novolak cyanate ester represented by the formula (8). Is more preferable. By using such a cyanate ester compound (C), a cured product that is superior in flame retardancy, has higher curability, and has a lower thermal expansion coefficient tends to be obtained.

  The content of the cyanate ester compound (C) is preferably 10 to 60 parts by mass, more preferably 10 to 55 parts by mass, and further preferably 10 to 50 parts by mass with respect to 100 parts by mass of the resin solid content. Part. When the content of the cyanate ester compound (C) is within the above range, it tends to be superior in heat resistance, low dielectric constant, low dielectric loss tangent, and the like.

(Epoxy resin (D))
The epoxy resin (D) is not particularly limited. For example, polyoxynaphthylene type epoxy resin, bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol A novolak. 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 novolak 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, trigly Diisocyanurate, glycidyl ester type epoxy resin, alicyclic epoxy resin, dicyclopentadiene novolak type epoxy resin, biphenyl novolac type epoxy resin, phenol aralkyl novolak type epoxy resin, naphthol aralkyl novolak type epoxy resin, aralkyl novolak type epoxy resin, Biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, butadiene epoxidized compound, hydroxyl group-containing silicone resin and Examples thereof include compounds obtained by reaction with epichlorohydrin or halides thereof. These epoxy resins can be used alone or in combination of two or more. Among these, polyoxynaphthylene type epoxy resins are preferable. By including such an epoxy resin (D), there exists a tendency for the flame retardance and heat resistance of the hardened | cured material obtained to improve more.

  The content of the epoxy resin (D) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 10 to 35 parts by mass with respect to 100 parts by mass of the resin solid content. is there. When the content of the epoxy resin (D) is within the above range, the adhesiveness and flexibility tend to be excellent.

(Phenolic resin (E))
Although it does not specifically limit as a phenol resin (E), For example, bisphenol A type phenol resin, bisphenol E type phenol resin, bisphenol F type phenol resin, bisphenol S type phenol resin, phenol novolak resin, bisphenol A novolak type phenol resin, Glycidyl ester type phenol resin, aralkyl novolac type phenol resin, biphenyl aralkyl type phenol resin, cresol novolac type phenol resin, polyfunctional phenol resin, naphthol resin, naphthol novolac resin, polyfunctional naphthol resin, anthracene type phenol resin, naphthalene skeleton modified novolak Type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopenta Ene type phenolic resin, biphenyl type phenol resins, alicyclic phenol resins, polyol-type phenolic resin, a phosphorus-containing phenol resin, a hydroxyl group-containing silicone resins and the like, but is not particularly limited. These phenol resins can be used individually by 1 type or in combination of 2 or more types.

  The content of the phenol resin (E) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, and further preferably 10 to 35 parts by mass with respect to 100 parts by mass of the resin solid content. is there. When the content of the phenol resin (E) is within the above range, the adhesiveness and flexibility tend to be excellent.

(Oxetane resin (F))
Although it does not specifically limit as oxetane resin (F), For example, alkyl oxetane, such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3,3-dimethyloxetane, 3-methyl-3 -Methoxymethyloxetane, 3,3'-di (trifluoromethyl) perfluoxetane, 2-chloromethyloxetane, 3,3-bis (chloromethyl) oxetane, biphenyl type oxetane, OXT-101 (trade name, manufactured by Toagosei Co., Ltd.) ), OXT-121 (trade name of 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 with respect to 100 parts by mass of the resin solid content. is there. When the content of the oxetane resin (F) is within the above range, the adhesiveness and flexibility tend to be superior.

(Benzoxazine compound (G))
Although it does not specifically limit as a benzoxazine compound (G), For example, bisphenol A type benzoxazine BA-BXZ (trade name made by Konishi Chemical) bisphenol F type benzoxazine BF-BXZ (trade name made by Konishi Chemical), 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.

  The content of the benzoxazine compound (G) 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 with respect to 100 parts by mass of the resin solid content. It is. When the content of the benzoxazine compound (G) is within the above range, it tends to be more excellent in heat resistance and the like.

(Compound having a polymerizable unsaturated group (H))
Although it does not specifically limit as a compound (H) which has a polymerizable unsaturated group, For example, vinyl compounds, such as ethylene, propylene, styrene, divinylbenzene, divinylbiphenyl; methyl (meth) acrylate, 2-hydroxyethyl (meta) ) 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 such as (meth) acrylates or monohydric or polyhydric alcohols; bisphenol A type epoxy (meth) acrylates, bisphenol F type epoxy (meth) acrylates, etc. Carboxymethyl (meth) acrylate; benzocyclobutene resin; (bis) maleimide resins. These compounds having a polymerizable unsaturated group can be used alone or in combination.

  The content of the polymerizable unsaturated group-containing compound (H) is preferably 10 to 45 parts by mass, more preferably 10 to 40 parts by mass, further preferably 100 parts by mass of the resin solid content. Is 10 to 35 parts by mass. When the content of the polymerizable unsaturated compound-containing compound (H) is within the above range, the heat resistance and toughness tend to be superior.

[Filler (I)]
The resin composition of this embodiment may further contain a filler (I). As the filler (I), known ones can be used as appropriate, and the kind thereof is not particularly limited, and inorganic fillers and / or organic fillers generally used in laminated plate applications are preferably used. Can do.

  Examples of the inorganic filler 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 sulfates such as barium sulfate; aluminum hydroxide, aluminum hydroxide heat-treated products (heating aluminum hydroxide) Treated and reduced in part of crystal water), 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 Olin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fiber (E glass, T glass, Including fine glass powders such as D glass, S glass, and Q glass), hollow glass, and spherical glass. An inorganic filler may be used individually by 1 type, or may use 2 or more types together. Among these, it is preferable to contain boehmite and / or silicas. By using such an inorganic filler, the thermal expansion coefficient tends to be further reduced.

  Examples of the organic filler include, but are not limited to, rubber powders such as styrene type, butadiene type, and acrylic type; core shell type rubber powder; silicone resin powder; silicone rubber powder; These fillers can be used individually by 1 type or in combination of 2 or more types as appropriate.

  Although content of filler (I) is not specifically limited, Preferably it is 50-300 mass parts with respect to 100 mass parts of resin solid content, More preferably, it is 75-250 mass parts, More preferably, 100 -200 parts by mass. When the content of the 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 or a wetting and dispersing agent. By including a silane coupling agent and a wetting and dispersing agent, the dispersibility of the filler, the resin component, the filler, and the adhesive strength of the substrate described later tend to be further improved.

  Although it will not specifically limit if it is a silane coupling agent generally used for the surface treatment of an inorganic substance as a silane coupling agent, For example, (gamma) -aminopropyl triethoxysilane, N-beta- (aminoethyl) -gamma Aminosilane compounds such as aminopropyltrimethoxysilane; Epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane; Acrylicsilane compounds such as γ-acryloxypropyltrimethoxysilane; N-β- (N- Cationic silane compounds such as vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride; phenylsilane compounds and the like. A silane coupling agent may be used individually by 1 type, or may use 2 or more types together.

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

[Curing accelerator]
The resin composition of this embodiment may further contain a curing accelerator. Although it does not specifically limit as a hardening accelerator, For example, 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, tertiary amines such as N-methylpiperidine; phenols such as phenol, xylenol, cresol, resorcin, catechol ; Organic metal salts such as lead naphthenate, lead stearate, zinc naphthenate, zinc octylate, tin oleate, dibutyltin malate, manganese naphthenate, cobalt naphthenate, iron acetylacetone; these organic metal salts are phenol, bisphenol, etc. Inorganic metal salts such as tin chloride, zinc chloride, and aluminum chloride; ditinyl tin oxide, and other organic tin compounds such as alkyl tin and alkyl tin oxide. Among these, triphenylimidazole promotes the curing reaction and is particularly preferable because it 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 the solvent, the viscosity at the time of preparing the resin composition is lowered, the handling property is further improved, and the impregnation property to the base material described later tends to be further improved.

  The solvent is not particularly limited as long as it can dissolve a part or all of the resin component in the resin composition. For example, ketones such as acetone, methyl ethyl ketone, and methyl cellosolve; aromatics such as toluene and xylene Group hydrocarbons; amides such as dimethylformamide; propylene glycol monomethyl ether and acetate thereof. A solvent may be used individually by 1 type, or may use 2 or more types together.

[Method for producing resin composition]
Although the manufacturing method of the resin composition of this embodiment is not specifically limited, For example, the method of mix | blending each component mentioned above in a solvent one by one and fully stirring is mentioned. At this time, in order to uniformly dissolve or disperse each component, known processes such as stirring, mixing, and kneading can be performed. Specifically, the dispersibility of the filler with respect to the resin composition can be improved by performing the stirring and dispersing treatment using a stirring tank provided with a stirrer having an appropriate stirring ability. The above stirring, mixing, and kneading treatment can be appropriately performed using, for example, a known device such as a ball mill or a bead mill for mixing, or a revolving or rotating mixing device.

  In preparing the resin composition, an organic solvent can be used as necessary. The kind of the 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.

[Use]
The said resin composition for electronic materials can be used suitably as a prepreg, a resin sheet, a metal foil tension laminated board, or a printed wiring board, and can be used suitably according to a printed wiring board use. Hereinafter, the prepreg, the resin sheet, the metal foil-clad laminate, or the printed wiring board will be described.

[Prepreg]
The prepreg of this embodiment has a base material and the resin composition impregnated or coated on the base material. The manufacturing method of a prepreg can be performed according to a conventional method, and is not specifically limited. For example, after impregnating or applying the resin component in the present embodiment to the base material, by semi-curing (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 the filler (I)) is preferably 30 to 90% by mass, more preferably 35 to 85% by mass, and preferably 40 to 80% with respect to the total amount of the prepreg. % By mass. When the content of the resin composition is within the above range, the moldability tends to be further improved.

(Base material)
It does not specifically limit as a base material, The well-known thing used for various printed wiring board materials can be selected suitably according to the intended use and performance, and can be used. Although it does not specifically limit as a specific example of the fiber which comprises a base material, For example, glass fibers, such as E glass, D glass, S glass, Q glass, spherical glass, NE glass, L glass, T glass; Quartz etc. Inorganic fibers other than glass: polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (Technola (registered trademark), Teijin Techno Products Limited Polyesters such as 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Kuraray Co., Ltd.), Zexion (registered trademark, manufactured by KB Selen), etc .; polyparaphenylene Benzoxazole (Zylon (registered trademark), manufactured by Toyobo Co., Ltd.), poly Organic fibers such as imide can be mentioned. Among these, from the viewpoint of a low thermal expansion coefficient, 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 individually by 1 type, or may use 2 or more types together.

Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, roving, a chopped strand mat, a surfacing mat, etc. are mentioned. The weaving method of the woven fabric is not particularly limited, and for example, plain weave, Nanako weave, twill weave and the like are known, and can be appropriately selected from these known ones depending on the intended use and performance. . In addition, a glass woven fabric whose surface is treated with a fiber-opening treatment or a silane coupling agent is preferably used. Although the thickness and mass of the substrate are not particularly limited, those having a thickness of about 0.01 to 0.3 mm are preferably used. In particular, from the viewpoint of strength and water absorption, the substrate is preferably a glass woven fabric having 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. More preferred.

(Resin sheet)
The resin sheet of this embodiment has a sheet base material and the resin composition laminated on one or both sides of the sheet base material. The resin sheet is used as one means of thinning, and for example, a thermosetting resin (inorganic filler) used for a prepreg or the like directly on a sheet substrate (support) such as a metal foil or a film. Including) can be applied and dried.

  Although it does not specifically limit as a sheet | seat base material, The well-known thing used for various printed wiring board materials can be used. Examples thereof include a polyimide film, a polyamide film, a polyester film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate (PBT) film, a polypropylene (PP) film, a polyethylene (PE) film, an aluminum foil, a copper foil, and a gold foil. Among these, electrolytic copper foil and PET film are preferable.

  Examples of the application method include a method in which a solution obtained by dissolving the resin composition of the present embodiment in a solvent is applied onto a sheet substrate with a bar coater, a die coater, a doctor blade, a baker applicator, or the like.

  The resin sheet is preferably a resin sheet obtained by applying the resin composition to a sheet base material and then semi-curing (B-stage). Specifically, for example, after applying the resin composition to a sheet base material such as copper foil, the resin sheet is semi-cured by a method of heating in a dryer at 100 to 200 ° C. for 1 to 60 minutes, The manufacturing method etc. are mentioned. The amount of the resin composition attached to the sheet substrate is preferably in the range of 1 to 300 μm in terms of the resin thickness of the resin sheet.

  The resin sheet can be used after being peeled 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 formed on one side or both sides of the insulating layer, and the insulating layer contains the resin composition. More specifically, a 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 selected from the group consisting of the prepreg and the resin sheet, and the metal foil.

  The insulating layer may be composed of the above resin composition, one prepreg, or a resin sheet, or may be a laminate of two or more of the above resin composition, prepreg, or resin sheet.

  The conductor layer can be a metal foil such as copper or aluminum. Although the metal foil used here will not be specifically limited if it is used for printed wiring board material, Well-known copper foils, such as a rolled copper foil and an electrolytic copper foil, are preferable. Moreover, although the thickness of a conductor layer is not specifically limited, 1-70 micrometers is preferable, More preferably, it is 1.5-35 micrometers.

The molding method and molding conditions of the metal foil-clad laminate are not particularly limited, and general techniques and conditions of a printed wiring board laminate and a multilayer board can be applied. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used at the time of forming a metal foil-clad laminate. 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. Also, a multilayer board can be formed by laminating and combining the above-described prepreg and a separately prepared wiring board for an inner layer.

[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 includes the resin composition. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern. The above metal foil-clad laminate has a low coefficient of thermal expansion, good moldability and chemical resistance, and is particularly effectively used as a printed wiring board for semiconductor packages that require such performance. Can do.

  Specifically, the printed wiring board of this embodiment can be manufactured by the following method, for example. First, the metal foil-clad laminate (such as a copper-clad laminate) is prepared. An inner layer circuit is formed by etching the surface of the metal foil-clad laminate to produce an inner layer substrate. If necessary, surface treatment is performed on the inner layer circuit surface of the inner layer substrate to increase the adhesive strength, then the required number of the prepregs are stacked on the inner layer circuit surface, and a metal foil for the outer layer circuit is laminated on the outer side. Then, it is integrally molded by heating and pressing. In this way, a multilayer laminate is produced in which an insulating layer made of a cured material of the base material and the thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit. Next, after this multi-layer laminate is subjected to drilling for through holes and via holes, desmear treatment is performed to remove smears, which are resin residues derived from the resin component contained in the cured product layer. . After that, a plated metal film is formed on the wall surface of this hole to connect the inner layer circuit and the metal foil for the outer layer circuit, and the outer layer circuit is formed by etching the metal foil for the outer layer circuit to produce a printed wiring board. Is done.

  For example, the above-described prepreg (the base material and the above-described resin composition attached thereto) and the metal foil-clad laminate resin composition layer (the layer made of the above-described resin composition) include the above-described resin composition. An insulating layer is formed.

  When a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer to be a circuit on the prepreg, the resin sheet, or the resin composition. At this time, a method of electroless plating can be used for forming the conductor layer.

  The printed wiring board of the present embodiment effectively suppresses the warp of the semiconductor plastic package by maintaining the excellent elastic modulus even under the reflow temperature at the time of mounting the semiconductor on the above-described insulating layer. It can be used particularly effectively as a printed wiring board.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited in any way by the following examples.

[Synthesis Example 1]
In the reactor, α-naphthol aralkyl type phenol resin (SN495V, OH group equivalent: 236 g / eq., Manufactured by Nippon Steel Chemical Co., Ltd.): The number of repeating units n of naphthol aralkyl includes 1 to 5. ) 0.47 mol (OH group equivalent) 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 0.93 mol of cyanogen chloride in chloroform was added dropwise to the reactor over 1.5 hours, and the mixture was stirred for 30 minutes after completion of the addition. Thereafter, a mixed solution of 0.1 mol of triethylamine and 30 g of chloroform was dropped into the reactor and stirred for 30 minutes to complete the reaction. After triethylamine hydrochloride formed as a by-product was filtered off from the reaction solution, the obtained filtrate was washed with 500 mL of 0.1N hydrochloric acid, and then washed with 500 mL of water four times. This was dried with sodium sulfate, evaporated at 75 ° C., and degassed at 90 ° C. under reduced pressure to obtain a brown solid α-naphthol aralkyl cyanate ester resin (SNCN). When the obtained α-naphthol aralkyl type cyanate ester resin was analyzed by infrared absorption spectrum, absorption of a cyanate ester group in the vicinity of 2264 cm ⁻¹ was confirmed.

[Example 1]
17.3 parts by mass of a novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 28.7 parts by mass of the naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, and 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 Moleculars 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 having a resin content of 44.5% by mass. A metal foil-clad laminate was prepared using the obtained prepreg, and the thermal expansion coefficient measured by the following TMA tension method is shown in Table 1.

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 It is a compound having an average molecular weight of 5000.

[Comparative Example 1]
24.6 parts by mass of a novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.), 36.8 parts by mass of the naphthol aralkyl cyanate ester resin obtained in Synthesis Example 1, and 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 size 1.5 μm, manufactured by Admatex Co., Ltd.), 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 having a resin content of 44.5% by mass. A metal foil-clad laminate was prepared using the obtained prepreg, and the thermal expansion coefficient measured by the following TMA tension method is shown in Table 1.

[Comparative Example 2]
12.7 parts by mass of a novolac 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 polyoxynaphthylene type 31.8 parts by mass of epoxy resin (HP-6000, manufactured by DIC Corporation), 24.6 parts by mass of bismaleimide compound (BMI-1000P, manufactured by Daiwa Kasei Kogyo Co., Ltd.) represented by the following formula, silica 120 parts by mass (SC-5050 MOB, average particle size 1.5 μm, manufactured by Admatechs Co., Ltd.) and 0.5 part by mass of 2,4,5-triphenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) To get 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 having a resin content of 44.5% by mass. A metal foil-clad laminate was prepared using the obtained prepreg, and the thermal expansion coefficient measured by the following TMA tension method is shown in Table 1.
(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, and 12 μm thick electrolytic copper foil (3EC-III, manufactured by Mitsui Mining & Smelting Co., Ltd.) was placed up and down, and the pressure was 30 kgf / Lamination was performed at 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 tension method)]
With respect to the obtained eight-layer metal foil-clad laminate, the thermal expansion coefficient of the glass cloth in the longitudinal direction was measured for the insulating layer of the laminate by the TMA method (Thermo-mechanical analysis) defined in JLSC 6481. The value was obtained. Specifically, after removing the copper foils on both sides of the metal foil-clad laminate obtained above by etching, measurement was carried out by a TMA tensile method using a thermomechanical analyzer (TA Instruments). In the TMA tensile method, the load was 2.5 g, the chuck was 10 mm, the temperature was raised from 40 ° C. to 340 ° C. at 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 type cyanate ester resin obtained in Synthesis Example 1, 50 parts by mass of a bismaleimide compound (BMI-3000J, manufactured by Designer Moleculars Inc.), silica (SC-5050MOB, average particle size 1.5 μm) 100 parts by mass of Admatechs Co., Ltd.) and 0.05 parts by mass of zinc octylate (Nippon Chemical Industry Co., Ltd.) were mixed to obtain a varnish. This varnish was diluted with methyl ethyl ketone, impregnated on a 0.1 mm thick T glass woven fabric, and dried by heating at 140 ° C. for 3 minutes to obtain a prepreg having a resin content of 50 mass%. Table 2 shows the results of producing a metal foil-clad laminate using the obtained prepreg and evaluating the physical properties by the following methods. The thermal expansion coefficient was measured by the TMA compression method.

In the bismaleimide compound (BMI-3000J), 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 weight A compound having an average molecular weight of 3000.

[Comparative Example 3]
In place of the bismaleimide compound (BMI-3000J), 50 parts by mass of a novolac maleimide compound (BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) was used, and the amount of zinc octylate used was 0.1 parts by mass. Except for the above, a prepreg having a resin content of 50% by mass was obtained in the same manner as in Example 2. Table 2 shows the results of producing a metal foil-clad laminate using the obtained prepreg and evaluating the physical properties by the following methods. The thermal expansion coefficient was measured by the TMA compression method.

[Production of metal foil-clad laminate]
Eight prepregs 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 up and down, with a pressure of 30 kgf / cm ² , 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〕
With respect to the obtained 8-layer metal foil-clad laminate, the glass transition temperature was measured by the DMA method with a dynamic viscoelasticity analyzer (TA Instruments) in accordance with JIS C6481.

[Thermal expansion coefficient (TMA compression method)]
With respect to the obtained eight-layer metal foil-clad laminate, the thermal expansion coefficient of the glass cloth in the longitudinal direction was measured for the insulating layer of the laminate by the TMA method (Thermo-mechanical analysis) defined in JLSC 6481. The value was obtained. Specifically, after removing the copper foil on both surfaces of the metal foil-clad laminate obtained above by etching, measurement was performed by a TMA compression method with a thermomechanical analyzer (TA Instruments). In the TMA compression method, the load was 5 g, the temperature was raised from 40 ° C. to 340 ° C. at 10 ° C. per minute, and the linear thermal expansion coefficient (ppm / ° C.) from 60 ° C. to 120 ° C. was measured.

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

[Laminated dielectric loss tangent]
Using the test piece (n = 1) from which the copper foil of the copper-clad laminate was removed, the dielectric loss tangent measurement of 2, 10 GHz was performed 3 times by the cavity resonator perturbation method (Agilent 8722ES, manufactured by Agilent Technologies), The average value was obtained.

[Thermal weight 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, in accordance with JIS K7120-1987, a differential thermothermal gravimetric simultaneous measurement device TG / DTA6200 (S.I.I.・ The test piece 3mm x 3mm x 0.8mm by Nanotechnology Co., Ltd., decrease in thermal weight when reaching 450 ° C when heated at a starting temperature of 300 ° C and a heating rate of 10 ° C / min under nitrogen flow The temperature at which the rate (thermal decomposition amount (%)) and the thermogravimetric reduction rate were 1% were determined based on the following formula.
Thermal weight loss rate (%) = (I−J) / I × 100
(I represents the weight at the starting temperature, and J represents the weight at 450 ° C.)

  The resin composition for electronic materials of the present invention has industrial applicability as a material for a prepreg, a resin sheet, a metal foil-clad laminate, or a printed wiring board.

Claims (17)

A bismaleimide compound (A),
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 linearly connected.
Resin composition for electronic materials.
The bismaleimide compound (A) further has one or more cyclic hydrocarbon groups that may contain a hetero atom having 4 to 10 atoms constituting the ring,
Each of the two maleimide groups is independently bonded to the cyclic hydrocarbon group via the first linking group in which 8 or more atoms are linearly linked;
Each of the polyimide groups is independently bonded to the cyclic hydrocarbon group via a second linking group in which 8 or more atoms are connected in a straight chain.
The resin composition for electronic materials according to claim 1. The cyclic hydrocarbon group is an alicyclic group;
The resin composition for electronic materials according to claim 2. The first linking group and / or the second linking group is a substituted or unsubstituted divalent hydrocarbon group.
The resin composition for electronic materials as described in any one of Claims 1-3. The bismaleimide compound (A) has a repeating unit represented by the following formula (2).
The resin composition for electronic materials as described in any one of Claims 1-4.
(In the formula, R ¹ and R ³ each independently represent a hydrocarbon group in which 8 or more atoms are linked in a straight chain, and R ² represents the number of atoms constituting the ring, which is substituted or unsubstituted. Represents a cyclic hydrocarbon group which 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 as described in any one of Claims 1-5.
(Wherein R ¹ and R ³ each independently represents a hydrocarbon group in which 8 or more atoms are linearly linked, and R ² each independently represents a substituted or unsubstituted ring. The cyclic hydrocarbon group which may contain a hetero atom having 4 to 10 atoms is included, and n represents a number of 1 to 10. The bismaleimide compound (A) has a weight average molecular weight of 1 × 10 ³ to 1 × 10 ⁴ .
The resin composition for electronic materials as described in any one of Claims 1-6. Maleimide compound (B) other than the bismaleimide compound (A), cyanate ester compound (C), epoxy resin (D), phenol resin (E), oxetane resin (F), benzoxazine compound (G), and polymerization Further including one or more selected from the group consisting of compounds (H) having a possible unsaturated group,
The resin composition for electronic materials as described in any one of Claims 1-7. Content of the said bismaleimide compound (A) is 5-60 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials as described in any one of Claims 1-8. Content of the said cyanate ester compound (C) is 10-60 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials according to claim 8 or 9. Content of the said epoxy resin (D) is 10-45 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials as described in any one of Claims 8-10. Further comprising a filler (I),
The resin composition for electronic materials as described in any one of Claims 1-11. Content of the said filler (I) is 50-300 mass parts with respect to 100 mass parts of resin solid content,
The resin composition for electronic materials according to claim 12. A substrate;
The resin composition for electronic materials according to any one of claims 1 to 13, which is impregnated or applied to the substrate.
Prepreg. A sheet substrate;
The resin composition for electronic materials according to any one of claims 1 to 13, which is laminated on one side or both sides of the sheet base material,
Resin sheet. An insulating layer;
A conductive layer laminated on one or both sides of the insulating layer,
The said insulating layer contains the resin composition for electronic materials as described in any one of Claims 1-13,
Metal foil-clad laminate. Having an insulating layer and a conductor layer formed on the surface of the insulating layer;
The said insulating layer contains the resin composition for electronic materials as described in any one of Claims 1-13,
Printed wiring board.