WO2019225482A1 - Resin varnish, prepreg, laminate, printed wiring board, and semiconductor package - Google Patents

Abstract

Provided is a resin varnish having high heat resistance, low relative permittivity, high metal foil adhesion, high glass transition temperature, and low thermal expansion properties, excellent moldability and plating uniformity, and also minimal fluctuation in the amount of dimensional variation. Also provided are a prepreg, a laminate, a printed wiring board, and a semiconductor package obtained using the resin varnish. The resin varnish comprises (A) a maleimide compound, (B) an epoxy resin, and (C) a copolymer resin having structural units derived from an aromatic vinyl compound and structural units derived from maleic anhydride, the maleimide compound (A) being a maleimide compound having an N-substituted maleimide group, obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound, and (a3) a diamine compound, and being obtained by reaction in which the usage ratio [(a2) component/(a3) component] (mole ratio) of the (a2) component to the (a3) component is 0.9-5.0.

Description

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

The present invention relates to a resin varnish, a prepreg, a laminated board, a printed wiring board, and a semiconductor package.

In recent years, in a mother board such as a multi-function mobile phone terminal, the wiring width (L) and spacing (S) of the printed wiring board (hereinafter referred to as wiring) along with higher speed communication, higher wiring density, and extremely thin printed wiring board. In some cases, the width and the interval are combined to be expressed as [L / S]). With such narrowing of L / S, it is becoming difficult to stably produce printed wiring boards with a high yield. Further, in the design of a conventional printed wiring board, a layer without a wiring pattern called a “skip layer” is provided in a part of layers in consideration of a communication failure or the like. As electronic devices become more sophisticated, the amount of wiring design increases and the number of printed wiring boards increases. However, the provision of the skip layer causes a problem that the thickness of the motherboard further increases. .
As a method for improving these problems, it is effective to lower the dielectric constant of an insulating material used for a printed wiring board. L / S can be easily controlled by reducing the relative dielectric constant of the insulating material. Therefore, L / S can be stably produced in a shape close to the current design, and the number of layers can be reduced by reducing skip layers. . Therefore, the insulating material used for the printed wiring board is required to have a material characteristic with a small relative dielectric constant.

In addition to multifunctional mobile phone terminals, for example, communication devices represented by servers, routers, mobile base stations, and the like have come to be used in a higher frequency band region. In addition, since high melting point lead-free solder has come to be used for soldering electronic components, the material of the substrate used for these is low dielectric constant and high glass transition temperature (high Tg). There is a tendency to demand a material having excellent reflow heat resistance.
In addition, a mother board used for a multifunctional mobile phone terminal or the like is required to be connected by a small-diameter laser via when connecting between layers as the wiring density increases and the pattern width narrows. From the viewpoint of connection reliability, filled plating is often used, and the connectivity at the interface between inner layer copper and plated copper is very important, so there is a tendency to improve the laser workability of the base material. .

It is common that a step of removing resin residual components (desmear treatment step) is performed after laser processing of the substrate. Since the desmear treatment is performed on the bottom surface and the wall surface of the laser via, when the resin component of the base material is dissolved in a large amount by the desmear treatment, the shape of the laser via may be remarkably deformed due to the dissolution of the resin. Various problems such as non-uniformity around the plating may occur. For this reason, it is required that the amount of the resin component of the base material dissolved by the desmear treatment, that is, the so-called desmear dissolution amount is an appropriate value.

In addition, regarding the interlayer connection by the small diameter laser via, one of the important characteristics is that the variation in the dimensional change amount of the base material is small. Along with the thinning of the motherboard, a multi-layer stacking method is required as a base material stacking method, and a plurality of heat amounts and stress during stacking are applied to the base material. Therefore, when the variation in the dimensional change amount of the substrate itself (meaning the variation in the heat shrinkage amount of the substrate) is large, a misalignment of vias connecting the layers may occur each time the layers are stacked. For this reason, it is required to stabilize the variation in the amount of heat shrinkage of the substrate.

Up to now, among various properties required for insulating materials used for printed wiring boards, for the purpose of reducing the dielectric constant, a method of containing an epoxy resin having a low relative dielectric constant, a method of introducing a cyanate group The method of containing polyphenylene ether has been used. For example, a resin composition containing an epoxy resin (see Patent Document 1), a resin composition containing polyphenylene ether and bismaleimide (see Patent Document 2), and a resin composition containing polyphenylene ether and a cyanate resin (patent Reference 3), a resin composition containing at least one of styrene-based thermoplastic elastomer and the like and / or triallyl cyanurate (see Patent Document 4), a resin composition containing polybutadiene (see Patent Document 5), polyphenylene A resin composition obtained by pre-reacting an ether resin, a polyfunctional maleimide and / or polyfunctional cyanate resin, and liquid polybutadiene (see Patent Document 6), and a compound having an unsaturated double bond group are provided. Or grafted polyphenylene ether and triallyl cyanurate and / or Resin composition containing allyl isocyanurate and the like (see Patent Document 7), reaction product of polyphenylene ether and unsaturated carboxylic acid or unsaturated acid anhydride, and polyfunctional maleimide and the like A thing (refer patent document 8) etc. are proposed.

JP 58-69046 A JP-A-56-133355 Japanese Patent Publication No. 61-18937 JP-A-61-286130 JP-A-62-148512 JP 58-164638 A Japanese Patent Laid-Open No. 2-208355 JP-A-6-179734

As described above, insulating materials used for printed wiring boards tend to be required to have various characteristics such as reducing the dielectric constant, and contain the resin composition described in Patent Documents 1 to 8. However, the prepreg has a relatively good dielectric constant, but there are many cases where the severe demands of the market in recent years cannot be satisfied. In addition, any of high heat resistance, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, plating rotability (laser processability), and small variation in dimensional variation is insufficient. In many cases, there is room for further improvement. In particular, according to the study by the present inventors, it has been found that the prepreg containing the conventional resin composition does not sufficiently suppress the variation in the amount of dimensional change. .

Therefore, the object of the present invention is to have high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, excellent formability and plating rotation, and dimensional change An object of the present invention is to provide a resin varnish having a small amount of variation, and to provide a prepreg, a laminate, a printed wiring board, and a semiconductor package obtained by using the resin varnish.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that “(A) a maleimide compound”, “(B) an epoxy resin”, and “(C) a copolymer resin having a specific structural unit”. And (A) the maleimide compound (A) is a specific maleimide compound to be described later, and found that the above-mentioned problems can be solved, and the present invention has been completed. . The present invention has been completed based on such knowledge.

The present invention relates to the following [1] to [15].
[1] (A) Maleimide compound,
(B) an epoxy resin, and (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride,
Containing
The (A) maleimide compound is obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound and (a3) a diamine compound. A maleimide compound having a group,
The (A) maleimide compound is reacted with the use ratio of the component (a2) to the component (a3) [component (a2) / component (a3)] (molar ratio) being 0.9 to 5.0. Resin varnish that can be obtained.
[2] The resin varnish according to [1], wherein the (a2) monoamine compound is represented by the following general formula (a2-1), and the (a3) diamine compound is represented by the following general formula (a3-1): .

(In General Formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^A4 may be the same And when u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.)

(In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl having 1 to 5 carbon atoms. A group, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)
[3] The above [1] or [3] wherein the relationship between the sum of —NH ₂ group equivalents of the component (a2) and the component (a3) and the maleimide group equivalent of the component (a1) satisfies the following formula: 2].
0.1 ≦ [maleimide group equivalent] / [-NH ₂ group equivalent] ≦ 10
[4] The component (B) is a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a naphthalene type epoxy resin, an anthracene type epoxy resin, a biphenyl type epoxy resin, a biphenyl aralkyl novolak type epoxy resin, and The resin varnish according to any one of the above [1] to [3], which is at least one selected from the group consisting of dicyclopentadiene type epoxy resins.
[5] The above-mentioned [1], wherein the component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii) ] The resin varnish according to any one of [4] to [4].

(Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)
[6] In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] ] (Molar ratio) is 1 to 9, the resin varnish according to any one of the above [1] to [4].
[7] The content of the components (A) to (C) is 15 to 65 parts by weight of the component (A) with respect to 100 parts by weight of the sum of the components (A) to (C). The resin varnish according to any one of the above [1] to [6], wherein is 15 to 50 parts by mass and component (C) is 10 to 45 parts by mass.
[8] The resin varnish according to any one of [1] to [7], further comprising (D) an inorganic filler.
[9] The resin varnish according to any one of [1] to [8], further comprising (E) a curing agent.
[10] The resin varnish according to any one of the above [1] to [9], further comprising (F) a flame retardant.
[11] A prepreg comprising the resin varnish according to any one of [1] to [10] above.
[12] The prepreg according to the above [11], wherein a standard deviation σ obtained according to the following method is 0.012% or less.
Standard deviation σ calculation method:
A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate with respect to the initial value of each measurement distance, and a standard deviation σ with respect to the average value is calculated.
[13] A laminate comprising the prepreg according to [11] or [12] and a metal foil.
[14] A printed wiring board comprising the prepreg according to [11] or [12] or the laminate according to [13].
[15] A semiconductor package in which a semiconductor element is mounted on the printed wiring board according to [14].

According to the present invention, it has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, excellent formability and plating rotation, and variation in dimensional change. A small resin varnish can be provided. Moreover, the prepreg, laminated board, printed wiring board, and semiconductor package which are obtained using this resin varnish can be provided.

It is a schematic diagram of the evaluation board | substrate used for the measurement of the variation in the dimensional change amount in an Example.

In the numerical range described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. Further, the lower limit value and the upper limit value of the numerical range can be arbitrarily combined with the lower limit value and the upper limit value of other numerical ranges, respectively.
Moreover, unless otherwise indicated, each component and material illustrated in this specification may be used individually by 1 type, and may use 2 or more types together. In the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Means.
Embodiments in which the items described in this specification are arbitrarily combined are also included in the present invention.

[Resin varnish]
The resin varnish of the present invention is as follows.
(A) a maleimide compound,
(B) an epoxy resin, and (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride,
Containing
The (A) maleimide compound is obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound and (a3) a diamine compound. A maleimide compound having a group,
The (A) maleimide compound is reacted with the use ratio of the component (a2) to the component (a3) [component (a2) / component (a3)] (molar ratio) being 0.9 to 5.0. Is obtained.

First, each component which a resin varnish contains is explained in full detail.
<(A) Maleimide compound>
Component (A) is a maleimide compound having the following N-substituted maleimide group (hereinafter sometimes referred to as maleimide compound (A)). Specifically, (a1) a maleimide compound having at least two N-substituted maleimide groups [hereinafter abbreviated as maleimide compound (a1)] and (a2) a monoamine compound [hereinafter abbreviated as monoamine compound (a2)]. And a (a3) diamine compound (hereinafter abbreviated as diamine compound (a3)), and a maleimide compound having an N-substituted maleimide group. In particular, the maleimide compound (A) is obtained by reacting the component (a2) and the component (a3) at a specific use ratio described later.

The weight average molecular weight (Mw) of the maleimide compound (A) is preferably 400 to 3,500, more preferably 400 to 2,000, and still more preferably 800 from the viewpoints of solubility in organic solvents and mechanical strength. ~ 1,500. In addition, the weight average molecular weight in this specification is a value measured by gel permeation chromatography (GPC) method (standard polystyrene conversion) using tetrahydrofuran as an eluent, and more specifically described in Examples. It is a value measured by the method.

(Maleimide compound (a1))
The maleimide compound (a1) is a maleimide compound having at least two N-substituted maleimide groups.
As the maleimide compound (a1), a maleimide compound having an aliphatic hydrocarbon group (but no aromatic hydrocarbon group is present) between any two maleimide groups among a plurality of maleimide groups [hereinafter referred to as fat Or a maleimide compound containing an aromatic hydrocarbon group between any two maleimide groups of the plurality of maleimide groups [hereinafter referred to as aromatic hydrocarbon group] Referred to as a containing maleimide]. Among these, an aromatic hydrocarbon group-containing maleimide is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating revolving property. The aromatic hydrocarbon group-containing maleimide only needs to contain an aromatic hydrocarbon group between any combination of two maleimide groups selected arbitrarily, and is also an aliphatic hydrocarbon together with the aromatic hydrocarbon group. It may have a group.
As maleimide compound (a1), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation, two or more per molecule Maleimide compounds having 5 N-substituted maleimide groups are preferred, and maleimide compounds having 2 N-substituted maleimide groups in one molecule are more preferred. Moreover, as a maleimide compound (a1), following general formula (a1) from a viewpoint of high heat resistance, a low dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion property, moldability, and plating revolving property. -1) to (a1-4), and more preferably an aromatic hydrocarbon group-containing maleimide represented by any of the following general formulas (a1-1), (a1-2) or (a1-4) The aromatic hydrocarbon group-containing maleimide represented by general formula (a1-2) is more preferred, and the aromatic hydrocarbon group-containing maleimide represented by the following general formula (a1-2) is particularly preferred.

In the above formula, R ^A1 to R ^A3 each independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^A1 represents an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, —O—, —C (═O) —, —S—, —SS— or a sulfonyl group. p, q, and r are each independently an integer of 0-4. s is an integer of 0 to 10.
Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^A1 to R ^A3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and n-pentyl group. The aliphatic hydrocarbon group is preferably 1 to 1 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating swirlability. 3 is an aliphatic hydrocarbon group, more preferably a methyl group or an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by X ^A1 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, and a 1,5-pentamethylene group. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, and plating rotation. Group, more preferably a methylene group.
Examples of the alkylidene group having 2 to 5 carbon atoms represented by X ^A1 include an ethylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group. Among these, an isopropylidene group is preferable from the viewpoints of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, and plating rotation.
X ^A1 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options. More preferred are as described above.
p, q, and r are each independently an integer of 0 to 4, and have high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, and roundness with plating. In view of the above, each is preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0.
s is an integer of 0 to 10, and is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability. In particular, the aromatic hydrocarbon group-containing maleimide represented by the general formula (a1-3) is preferably a mixture in which s is 0 to 3.

Specific examples of the maleimide compound (a1) include N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, bis (4-maleimidocyclohexyl) methane, and 1,4-bis (maleimide). Methyl) cyclohexane or other aliphatic hydrocarbon group-containing maleimide; N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3- (2-methylphenylene)] bismaleimide, N, N ′-[1,3- (4-methylphenylene)] bismaleimide, N, N ′-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4- Maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, bis (4-maleimide) Phenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis ( Maleimidomethyl) cyclohexane, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- ( 4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-Maleimidophenoxy) phenyl] ethane, 1,2-bis [4- ( -Maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [ 4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4 ′ -Bis (3-maleimidophenoxy) biphenyl, 4,4'-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy) pheny Ru] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) ) Phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4 -(4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4- Maleimidophenoxy) -α, α-dimethylbenzyl] benze 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3 , 5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenyl An aromatic hydrocarbon group-containing maleimide such as methanemaleimide may be mentioned.

Among these, from the viewpoint of high reaction rate and higher heat resistance, bis (4-maleimidophenyl) methane, bis (4-maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4 -Maleimidophenyl) disulfide, N, N ′-(1,3-phenylene) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane are preferred, and bis (4-Maleimidophenyl) methane and N, N ′-(1,3-phenylene) bismaleimide are preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in organic solvents.
As the maleimide compound (a1), one type may be used alone, or two or more types may be used in combination.

(Monoamine compound (a2))
The monoamine compound (a2) is not particularly limited as long as it is a compound having one amino group, but has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, From the viewpoints of plating circulation and dimensional variation, monoamine compounds having an acidic substituent are preferred, and monoamine compounds represented by the following general formula (a2-1) are preferred.

In the general formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group. R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5 is satisfied. However, when t is an integer of 2 to 5, a plurality of R ^A4 may be the same or different. When u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.
The acidic substituent represented by R ^A4 is preferably a hydroxyl group or a carboxy group from the viewpoint of solubility and reactivity, and more preferably a hydroxyl group in consideration of heat resistance.
t is an integer of 1 to 5, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, roundness with plating, and dimensional variation. , Preferably an integer of 1 to 3, more preferably 1 or 2, and still more preferably 1.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Can be mentioned. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the halogen atom represented by R ^A5 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
u is an integer of 0 to 4, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, formability, roundness with plating, and dimensional variation. , Preferably an integer of 0 to 3, more preferably an integer of 0 to 2, even more preferably 0 or 1, and particularly preferably 0.
As the monoamine compound (a2), from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability, plating rotation and dimensional variation. A monoamine compound represented by the following general formula (a2-2) or (a2-3) is more preferable, and a monoamine compound represented by the following general formula (a2-2) is more preferable. However, R ^A4 , R ^A5 and u in the general formulas (a2-2) and (a2-3) are the same as those in the general formula (a2-1), and preferred ones are also the same.

Examples of the monoamine compound (a2) include o-aminophenol, m-aminophenol, p-aminophenol, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-aminobenzenesulfonic acid, Examples thereof include monoamine compounds having an acidic substituent, such as m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, and 3,5-dicarboxyaniline.
Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and reactivity, and o-aminophenol from the viewpoint of heat resistance. M-aminophenol and p-aminophenol are preferable, and p-aminophenol is more preferable in consideration of dielectric properties, low thermal expansibility and production cost.
A monoamine compound (a2) may be used individually by 1 type, and may use 2 or more types together.

(Diamine compound (a3))
The diamine compound (a3) is not particularly limited as long as it is a compound having two amino groups, but has high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low thermal expansion, moldability, From the viewpoint of variation in plating rotability and dimensional change, a diamine compound represented by the following general formula (a3-1) is preferable.

(Wherein X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a hydroxyl group. Represents a carboxy group or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group of X ^A2 carbon number of 1 to 3 shown, for example, methylene group, ethylene group, propylene group, propylidene group, and the like.
X ^A2 is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methylene group.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^A6 and R ^A7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
v and w are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.

The diamine compound (a3) is preferably a diamine compound represented by the following general formula (a3-1 ′).

(In the formula, X ^A2 , R ^A6 , R ^A7 , v and w are the same as those in the general formula (a3-1), and preferred embodiments are also the same.)

Specific examples of the diamine compound (a3) include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenylpropane, 2,2′-bis (4, 4'-diaminodiphenyl) propane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- Diaminodiphenylethane, 3,3'-diethyl-4,4'-diaminodiphenylethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylthioether, 3,3'-dihydroxy-4,4'-diamino Diphenylmethane, 2,2 ', 6,6'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-di Loro-4,4′-diaminodiphenylmethane, 3,3′-dibromo-4,4′-diaminodiphenylmethane, 2,2 ′, 6,6′-tetrachloro-4,4′-diaminodiphenylmethane, 2,2 ′ , 6,6′-tetrabromo-4,4′-diaminodiphenylmethane and the like. Among these, 4,4′-diaminodiphenylmethane and 3,3′-diethyl-4,4′-diaminodiphenylmethane are preferable from the viewpoint of inexpensiveness, and 4,4′- from the viewpoint of solubility in a solvent. Diaminodiphenylmethane is more preferred.

The reaction of the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3) is preferably carried out by reacting at a reaction temperature of 70 to 200 ° C. for 0.1 to 10 hours in the presence of an organic solvent. preferable.
The reaction temperature is more preferably 70 to 160 ° C., further preferably 70 to 130 ° C., and particularly preferably 80 to 120 ° C.
The reaction time is more preferably 1 to 6 hours, still more preferably 1 to 4 hours.

(Use amount of maleimide compound (a1), monoamine compound (a2) and diamine compound (a3))
Further, in the reaction of the maleimide compound (a1), the monoamine compound (a2) and the diamine compound (a3), the three amounts used are equivalent to the —NH ₂ group equivalent (first order) of the monoamine compound (a2) and the diamine compound (a3). The relationship between the sum of the primary amino group equivalents) and the maleimide group equivalents of the maleimide compound (a1) preferably satisfies the following formula.
0.1 ≦ [maleimide group equivalent] / [-NH ₂ group equivalent] ≦ 10
Thus, by setting [maleimide group equivalent] / [-NH ₂ group equivalent] to 0.1 or more, gelation and heat resistance do not decrease, and by setting it to 10 or less, This is preferable because the solubility in an organic solvent, metal foil adhesion, and heat resistance do not decrease.
From the same viewpoint, more preferably,
1 ≦ [maleimide group equivalent] / [total sum of —NH ₂ group equivalents] ≦ 9, more preferably
2 ≦ [maleimide group equivalent] / [total of —NH ₂ group equivalent] ≦ 8.

(Use ratio of monoamine compound (a2) and diamine compound (a3))
In the present invention, the (A) maleimide compound has a use ratio [(a2) component / (a3) component] (molar ratio) of the monoamine compound (a2) to the diamine compound (a3) of 0.9 to 5.0. By being obtained by the reaction, the variation in the dimensional change is remarkably reduced. The mechanism by which this effect appears is not clear. Even if the use ratio is less than 0.9 or more than 5.0, the dimensional variation varies greatly. From the same viewpoint, the use ratio is preferably 1.0 to 4.5, more preferably 1.0 to 4.0, and may be 1.5 to 3.5. It may be 3.0 or 1.5 to 2.5.
By reacting at the use ratio as described above, the ratio (molar ratio) between the structural unit derived from the monoamine compound (a2) and the structural unit derived from the diamine compound (a3) in the component (A) is 0.9 to 5.0, preferably 1.0 to 4.5, more preferably 1.0 to 4.0, and can be 1.5 to 3.5, or 1.5 to 3.0. You can also.

(Organic solvent)
The reaction of the maleimide compound (a1), monoamine compound (a2) and diamine compound (a3) is preferably performed in an organic solvent.
The organic solvent is not particularly limited as long as it does not adversely affect the reaction. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran; toluene, xylene, mesitylene Aromatic solvents such as dimethylformamide, dimethylacetamide, nitrogen atom-containing solvents including amide solvents such as N-methylpyrrolidone; sulfur atom-containing solvents including sulfoxide solvents such as dimethylsulfoxide; ethyl acetate, γ- Examples thereof include ester solvents such as butyrolactone. Among these, alcohol solvents, ketone solvents, and ester solvents are preferable from the viewpoint of solubility, and cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, and γ-butyrolactone are more preferable from the viewpoint of low toxicity. In view of the fact that it is highly soluble and hardly remains as a residual solvent during the production of prepreg, cyclohexanone, propylene glycol monomethyl ether, and dimethylacetamide are more preferable, and dimethylacetamide is particularly preferable.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Although there is no restriction | limiting in particular in the usage-amount of an organic solvent, Preferably it is 25 with respect to a total of 100 mass parts of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) from a viewpoint of solubility and reaction efficiency. The amount may be ˜1,000 parts by mass, more preferably 40 to 700 parts by mass, and still more preferably 60 to 250 parts by mass. By making it 25 parts by mass or more with respect to a total of 100 parts by mass of the maleimide compound (a1), monoamine compound (a2), and diamine compound (a3), it tends to ensure the solubility, and 1,000 parts by mass or less. By doing, it tends to be easy to suppress a significant decrease in reaction efficiency.
The organic solvent may be contained in the resin varnish of the present invention.

(Reaction catalyst)
You may implement reaction of a maleimide compound (a1), a monoamine compound (a2), and a diamine compound (a3) in presence of a reaction catalyst as needed. Examples of the reaction catalyst include amine-based catalysts such as triethylamine, pyridine, and tributylamine; imidazole-based catalysts such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine.
A reaction catalyst may be used individually by 1 type, and may use 2 or more types together.
The amount of the reaction catalyst used is not particularly limited, but is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total mass of the maleimide compound (a1) and the monoamine compound (a2).

<(B) Epoxy resin>
The component (B) is an epoxy resin (hereinafter sometimes referred to as an epoxy resin (B)), preferably an epoxy resin having at least two epoxy groups in one molecule.
Examples of the epoxy resin having at least two epoxy groups in one molecule include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, and glycidyl ester type epoxy resins. Among these, a glycidyl ether type epoxy resin is preferable.
The epoxy resin (B) is classified into various epoxy resins depending on the main skeleton, and in each of the above-mentioned types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, etc. Bisphenol type epoxy resin; biphenyl aralkyl novolak type epoxy resin, phenol novolak type epoxy resin, alkylphenol novolak type epoxy resin, cresol novolac type epoxy resin, naphthol alkylphenol copolymer novolak type epoxy resin, naphthol aralkyl cresol copolymer novolak type epoxy resin, Bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin and other novolac epoxy resins; stilbene epoxy Resin; Triazine skeleton-containing epoxy resin; Fluorene skeleton-containing epoxy resin; Naphthalene-type epoxy resin; Anthracene-type epoxy resin; Triphenylmethane-type epoxy resin; Biphenyl-type epoxy resin; Xylylene-type epoxy resin; Dicyclopentadiene-type epoxy resin It is classified into alicyclic epoxy resin.

Among these, from the viewpoint of high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature, low thermal expansion, moldability and plating rotation, bisphenol F type epoxy resin, phenol novolac type epoxy resin Preferably, at least one selected from the group consisting of cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenylaralkyl novolak type epoxy resin and dicyclopentadiene type epoxy resin, and low thermal expansion Cresol novolac type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and phenol novolac type More preferably at least one selected from the group consisting of epoxy resin, more preferably a cresol novolak type epoxy resin.
An epoxy resin (B) may be used individually by 1 type, and may use 2 or more types together.

The epoxy equivalent of the epoxy resin (B) is preferably 100 to 500 g / eq, more preferably 120 to 400 g / eq, still more preferably 140 to 300 g / eq, and particularly preferably 170 to 240 g / eq.
Here, the epoxy equivalent is the mass of the resin per epoxy group (g / eq), and can be measured according to the method defined in JIS K 7236 (2001). Specifically, using an automatic titrator “GT-200 type” manufactured by Mitsubishi Chemical Analytech Co., Ltd., weigh 2 g of epoxy resin into a 200 ml beaker, drop 90 ml of methyl ethyl ketone, dissolve in an ultrasonic cleaner, It is obtained by adding 10 ml of acetic acid and 1.5 g of cetyltrimethylammonium bromide and titrating with a 0.1 mol / L perchloric acid / acetic acid solution.
As a commercially available product of the epoxy resin (B), a cresol novolac type epoxy resin “EPICLON (registered trademark) N-673” (manufactured by DIC Corporation, epoxy equivalent: 205 to 215 g / eq), a naphthalene type epoxy resin “HP-4032” (Mitsubishi Chemical Corporation, epoxy equivalent: 152 g / eq), biphenyl type epoxy resin “YX-4000” (Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq), dicyclopentadiene type epoxy resin “HP-7200H” (DIC Corporation, epoxy equivalent; 280 g / eq) and the like. The epoxy equivalent is a value described in the catalog of the product manufacturer.

<(C) Specific copolymer resin>
Component (C) is a copolymer resin having a structural unit derived from a substituted vinyl compound and a structural unit derived from maleic anhydride (hereinafter sometimes referred to as copolymer resin (C)). Examples of the substituted vinyl compound include aromatic vinyl compounds, aliphatic vinyl compounds, and functional group-substituted vinyl compounds. Examples of the aromatic vinyl compound include styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like. Examples of the aliphatic vinyl compound include propylene, butadiene, isobutylene and the like. Examples of the functional group-substituted vinyl compound include acrylonitrile; a compound having a (meth) acryloyl group such as methyl acrylate and methyl methacrylate.
Among these, as the substituted vinyl compound, an aromatic vinyl compound is preferable, and styrene is more preferable.
As the component (C), a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii) is preferable.

(Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^C1 and R ^C2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ^C2 include an allyl group and a crotyl group. The alkenyl group is preferably an alkenyl group having 3 to 5 carbon atoms, more preferably an alkenyl group having 3 or 4 carbon atoms.
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^C2 include a phenyl group, a naphthyl group, an anthryl group, and a biphenylyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms.
x is preferably 0 or 1, more preferably 0.
In the structural unit represented by the general formula (Ci), R ^C1 is a hydrogen atom and x is 0, derived from the structural unit represented by the following general formula (Ci-1), that is, styrene The structural unit is preferred.

Content ratio of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C) [structural unit derived from the substituted vinyl compound / structural unit derived from maleic anhydride] (mol) The ratio is preferably from 1 to 9, more preferably from 2 to 9, even more preferably from 3 to 8, particularly preferably from 3 to 7. The content ratio of the structural unit represented by the general formula (Ci) to the structural unit represented by the formula (C-ii) [(Ci) / (Cii)] (molar ratio) Similarly, it is preferably 1 to 9, more preferably 2 to 9, further preferably 3 to 8, and particularly preferably 3 to 7. If the molar ratio is 1 or more, preferably 2 or more, the effect of improving the dielectric properties tends to be sufficient, and if it is 9 or less, the compatibility tends to be good.
The total content of the structural unit derived from the substituted vinyl compound and the structural unit derived from maleic anhydride in the copolymer resin (C), and the structural unit represented by the general formula (Ci) and the formula ( The total content of the structural unit represented by C-ii) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and particularly preferably substantially 100% by mass. %.
The weight average molecular weight (Mw) of the copolymer resin (C) is preferably 4,500 to 18,000, more preferably 5,000 to 18,000, more preferably 6,000 to 17,000, still more preferably. It is 8,000 to 16,000, particularly preferably 8,000 to 15,000, most preferably 9,000 to 13,000.

In addition, the technique for lowering the dielectric constant of an epoxy resin by using a copolymer resin of styrene and maleic anhydride, when applied to a printed wiring board material, results in insufficient impregnation into the substrate and copper foil peel strength. Therefore, it generally tends to be avoided. For this reason, the use of the copolymer resin (C) generally tends to be avoided, but in the present invention, the component (A) and the component (B) are used while using the copolymer resin (C). By containing the component and the component (D), it has high heat resistance, low relative dielectric constant, high metal foil adhesiveness, high glass transition temperature and low thermal expansion, and has formability, plating-around property and dimensions. It became an excellent resin varnish with little variation in variation.

(Method for producing copolymer resin (C))
The copolymer resin (C) can be produced by copolymerizing a substituted vinyl compound and maleic anhydride.
The substituted vinyl compound is as described above. A substituted vinyl compound may be used individually by 1 type, and may use 2 or more types together. In addition to the substituted vinyl compound and maleic anhydride, various polymerizable components may be copolymerized.
In addition, substituents such as allyl groups, methacryloyl groups, acryloyl groups, and hydroxy groups are introduced into the substituted vinyl compounds, particularly aromatic vinyl compounds, through Friedel-Crafts reactions or reactions using metal catalysts such as lithium. May be.

Commercial products can also be used as the copolymer resin (C). Examples of commercially available products include “SMA (registered trademark) 1000” (styrene / maleic anhydride = 1, Mw = 5,000), “SMA (registered trademark) EF30” (styrene / maleic anhydride = 3, Mw = 9,500), "SMA (registered trademark) EF40" (styrene / maleic anhydride = 4, Mw = 11,000), "SMA (registered trademark) EF60" (styrene / maleic anhydride = 6, Mw = 11, 500), “SMA (registered trademark) EF80” (styrene / maleic anhydride = 8, Mw = 14,400) [above, manufactured by CRAY VALLEY Co., Ltd.].

<(D) Inorganic filler>
The resin varnish of the present invention preferably contains an inorganic filler as the component (D) from the viewpoint of low thermal expansion.
Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, and barium titanate. Strontium titanate, calcium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, silica is preferable from the viewpoint of lowering the thermal expansion coefficient.
Examples of the silica include precipitated silica produced by a wet method and having a high water content, and dry method silica produced by a dry method and containing almost no bound water or the like. Examples of the dry process silica include crushed silica, fumed silica, and fused silica (fused spherical silica) depending on the production method. Silica is preferably fused silica from the viewpoint of low thermal expansibility and high fluidity when filled in a resin.

The average particle diameter of the inorganic filler, particularly silica, is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.1 to 6 μm, further preferably 0.1 to 3 μm, and 1 to 3 μm is particularly preferable. By making the average particle diameter of the inorganic filler, especially silica, 0.1 μm or more, the fluidity when highly filled can be kept good, and by making it 10 μm or less, the mixing probability of coarse particles can be increased. It is possible to reduce the occurrence of defects due to coarse particles. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when the cumulative frequency distribution curve by the particle diameter is obtained with the total volume of the particles being 100%, and a laser diffraction scattering method is used. It can be measured with a particle size distribution measuring device.
The specific surface area of the inorganic filler, particularly silica, is preferably 4 cm ² / g or more, more preferably 4 to 9 cm ² / g, and still more preferably 5 to 7 cm ² / g.

Among the inorganic fillers, in particular, in the case of a surface-treated inorganic filler, in addition to the effect of improving the low thermal expansion, the adhesion with the components (A) to (C) is improved. Since the dropout of the inorganic filler itself is suppressed, an effect of suppressing the deformation of the laser via shape due to excessive desmear tends to be obtained. In addition, it is more preferable that the inorganic filler is a surface-treated inorganic filler because the tendency to improve the plating and the variation in the dimensional change amount tends to be small. By making the inorganic filler a surface-treated inorganic filler, the plating reversibility is improved because the amount of desmear dissolution increases, and the laser hole wall surface unevenness and the glass cloth pop out tend to be a hole shape. I guess it is because there is.

Examples of the surface treatment agent that can be used to surface-treat the inorganic filler include, for example, an aminosilane coupling agent, an epoxysilane coupling agent, a phenylsilane coupling agent, an alkylsilane coupling agent, and an alkenylsilane. Coupling agent, alkynylsilane coupling agent, haloalkylsilane coupling agent, siloxane coupling agent, hydrosilane coupling agent, silazane coupling agent, alkoxysilane coupling agent, chlorosilane coupling agent, ( (Meth) acryl silane coupling agents, isocyanurate silane coupling agents, ureido silane coupling agents, mercapto silane coupling agents, sulfide silane coupling agents or isocyanate silane coupling agents. It is below. A surface treating agent may be used individually by 1 type, and may use 2 or more types together.
From the viewpoint of improving the adhesiveness with the components (A) to (C), and improving the rotability with plating and reducing the variation in dimensional change, an aminosilane coupling agent is used as the surface treatment agent. preferable. That is, as the component (D), an inorganic filler treated with an aminosilane coupling agent is preferable.
As the aminosilane coupling agent, a silane coupling agent having a silicon-containing group represented by the following general formula (D-1) and an amino group is preferable.

(Wherein R ^D1 is an alkyl group having 1 to 3 carbon atoms or an acyl group having 2 to 4 carbon atoms. Y is an integer of 0 to 3)

^Examples of the alkyl group having 1 to 3 carbon atoms represented by R ^D1 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Among these, a methyl group is preferable.
^Examples of the acyl group having 2 to 4 carbon atoms represented by RD1 include an acetyl group, a propionyl group, and an acrylic group. Among these, an acetyl group is preferable.

The aminosilane coupling agent may have one amino group, two amino groups, or three or more, but usually one amino group or Have two.
Examples of aminosilane coupling agents having one amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl- Examples thereof include N- (1,3-dimethyl-butylidene) propylamine and 2-propynyl [3- (trimethoxysilyl) propyl] carbamate, but are not particularly limited thereto.
Examples of aminosilane coupling agents having two amino groups include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, Examples include 1- [3- (trimethoxysilyl) propyl] urea and 1- [3- (triethoxysilyl) propyl] urea, but are not particularly limited thereto.

Further, a surface-treated inorganic filler and a surface-treated inorganic filler may be used in combination. In this case, although not particularly limited, the content of the inorganic filler not surface-treated is preferably 50 parts by mass or less, more preferably 30 parts relative to 100 parts by mass of the surface-treated inorganic filler. It is not more than part by mass, more preferably not more than 15 parts by mass, particularly preferably not more than 10 parts by mass, most preferably not more than 5 parts by mass.

<(E) Curing agent>
The resin varnish may further contain a curing agent (hereinafter sometimes referred to as a curing agent (E)) as the component (E). Examples of the curing agent (E) include dicyandiamide; chain aliphatic amines other than dicyandiamide, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, tetramethylguanidine, triethanolamine; Isophoronediamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, bis (4-amino-3-methyldicyclohexyl) methane, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8 , 10-tetraoxaspiro [5.5] undecane and other cyclic aliphatic amines; xylenediamine, phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and other aromatic amines And the like. Among these, dicyandiamide is preferable from the viewpoints of metal foil adhesion and low thermal expansion.
The dicyandiamide is represented by H ₂ N—C (═NH) —NH—CN, and the melting point is usually 205 to 215 ° C., and higher purity is 207 to 212 ° C. Dicyandiamide is a crystalline substance and may be orthorhombic or plate-like. Dicyandiamide preferably has a purity of 98% or more, more preferably has a purity of 99% or more, and still more preferably has a purity of 99.4% or more. As dicyandiamide, commercially available products can be used. For example, commercially available products such as those manufactured by Nippon Carbide Industries Co., Ltd., Tokyo Chemical Industry Co., Ltd., Kishida Chemical Co., Ltd., and Nacalai Tesque Co., Ltd. can be used. .

<(F) Flame retardant>
The resin varnish may further contain a flame retardant (hereinafter sometimes referred to as a flame retardant (F)) as the component (F). Here, among the curing agents, dicyandiamide and the like also have an effect as a flame retardant, but in the present invention, those that can function as a curing agent are classified as curing agents and are not included in the component (F). .
Examples of the flame retardant include halogen-containing flame retardants containing bromine, chlorine, etc .; phosphorus flame retardants; nitrogen flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, melamine cyanurate; cyclophosphazene, poly Examples thereof include phosphazene flame retardants such as phosphazene; inorganic flame retardants such as antimony trioxide. Among these, a phosphorus flame retardant is preferable.
Examples of the phosphorus flame retardant include an inorganic phosphorus flame retardant and an organic phosphorus flame retardant.
Examples of inorganic phosphorus flame retardants include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; inorganic nitrogen-containing phosphorus compounds such as phosphate amides Phosphoric acid; phosphine oxide and the like.
Examples of organic phosphorus flame retardants include aromatic phosphate esters, monosubstituted phosphonic acid diesters, disubstituted phosphinic acid esters, disubstituted phosphinic acid metal salts, organic nitrogen-containing phosphorus compounds, cyclic organophosphorus compounds, Examples thereof include phosphorus-containing phenol resins. Among these, aromatic phosphate esters and metal salts of disubstituted phosphinic acids are preferred. Here, the metal salt is preferably any one of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and preferably an aluminum salt. Among organic phosphorus flame retardants, aromatic phosphates are more preferable.

Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, resorcinol bis (diphenyl phosphate), 1,3 -Phenylenebis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylenebis (diphenyl phosphate) and the like.
Examples of monosubstituted phosphonic acid diesters include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphinate and methyl diphenylphosphinate.
Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid, and the like. As described above, these metal salts are preferably any of lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, and zinc salt.
Examples of the organic nitrogen-containing phosphorus compound include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and the like.
Examples of the cyclic organophosphorus compound include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa- And 10-phosphaphenanthrene-10-oxide.
Among these, at least one selected from an aromatic phosphate ester, a metal salt of a disubstituted phosphinic acid and a cyclic organic phosphorus compound is preferable, and an aromatic phosphate ester is more preferable.

The aromatic phosphate ester is preferably an aromatic phosphate ester represented by the following general formula (F-1) or (F-2), and is represented by the following general formula (F-1). More preferably, it is an aromatic phosphate ester. The metal salt of the disubstituted phosphinic acid is preferably a metal salt of a disubstituted phosphinic acid represented by the following general formula (F-3).

(Wherein R ^F1 to R ^F5 are each independently an alkyl group having 1 to 5 carbon atoms or a halogen atom. E and f are each independently an integer of 0 to 5, and g, h and i are each It is an integer of 0 to 4 independently.
R ^F6 and R ^F7 are each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 14 carbon atoms. M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, a titanium atom, or a zinc atom. j is an integer of 1 to 4. )

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F1 to R ^F5 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups and the like. The alkyl group is preferably an alkyl group having 1 to 3 carbon atoms. Examples of the halogen atom represented by R ^F1 to R ^F5 include a fluorine atom.
e and f are preferably integers of 0 to 2, and more preferably 2. g, h and i are preferably integers of 0 to 2, more preferably 0 or 1, and still more preferably 0.
^Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^F6 and R ^F7 include the same groups as in R ^F1 to R ^F5 .
Examples of the aryl group having 6 to 14 carbon atoms represented by R ^F6 and R ^F7 include a phenyl group, a naphthyl group, a biphenylyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aryl group having 6 to 10 carbon atoms.
j is equal to the valence of the metal ion, that is, varies within the range of 1 to 4 corresponding to the type of M.
M is preferably an aluminum atom. In addition, j is 3 when M is an aluminum atom.

(Content of each component of resin varnish)
The content of the components (A) to (C) in the resin varnish is not particularly limited, but the amount of the component (A) is 15 to 100 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). 65 parts by mass, (B) component is preferably 15-50 parts by mass, and (C) component is preferably 10-45 parts by mass. The total content of the components (A) to (C) is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass in the resin varnish (however, excluding the component (D) here). % Or more is more preferable.
When the component (A) is 15 parts by mass or more with respect to 100 parts by mass of the sum of the components (A) to (C), it is excellent in high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion. Further, the variation in the dimensional change amount tends to be small. On the other hand, when it is 65 parts by mass or less, the fluidity and moldability of the resin varnish tend to be good. From the same viewpoint, the content of the component (A) may be 25 to 65 parts by mass with respect to 100 parts by mass of the sum of the components (A) to (C).
When the component (B) is 15 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high heat resistance, high glass transition temperature and low thermal expansion tend to be obtained. On the other hand, when it is 50 parts by mass or less, it tends to be high heat resistance, low relative dielectric constant, high glass transition temperature, and low thermal expansion. From the same viewpoint, the content of the component (B) may be 20 to 45 parts by mass with respect to 100 parts by mass of the sum of the components (A) to (C).
When the component (C) is 10 parts by mass or more with respect to 100 parts by mass of the sum of the components (A) to (C), high heat resistance and a low relative dielectric constant tend to be obtained. On the other hand, when the amount is 45 parts by mass or less, high heat resistance, high metal foil adhesion, and low thermal expansion tend to be obtained. The content of the component (C) may be 10 to 30 parts by mass or 20 to 45 parts by mass with respect to 100 parts by mass of the sum of the components (A) to (C).
Further, although not particularly limited, when the resin varnish of the present invention contains the component (D), the content thereof is 30 to 70 with respect to 100 parts by mass of the total of the components (A) to (C). It is preferable that it is a mass part. (D) It exists in the tendency for the outstanding low thermal expansibility to be acquired because a component is 30 mass parts or more. On the other hand, when it is 70 parts by mass or less, heat resistance is obtained and the fluidity and moldability of the resin varnish tend to be good. From the same viewpoint, the content of the component (D) may be 40 to 60 parts by mass with respect to 100 parts by mass of the sum of the components (A) to (C).

When the component (E) is contained in the resin varnish, the content is preferably 0.5 to 6 parts by mass with respect to 100 parts by mass as the total of the components (A) to (C).
When the component (E) is 0.5 parts by mass or more with respect to 100 parts by mass of the total of the components (A) to (C), high metal foil adhesion and excellent low thermal expansion tend to be obtained. On the other hand, when it is 6 parts by mass or less, high heat resistance tends to be obtained.

When the component (F) is contained in the resin varnish, the content thereof is preferably 0.1 to 20 with respect to 100 parts by mass of the total of the components (A) to (C) from the viewpoint of flame retardancy. Part by mass, more preferably 0.5 to 10 parts by mass. In particular, when a phosphorus-based flame retardant is used as the component (F), from the viewpoint of flame retardancy, the phosphorus atom content is 0.1 to 3 masses per 100 mass parts of the total of the components (A) to (C). Is preferably 0.2 to 3 parts by mass, more preferably 0.5 to 3 parts by mass.

(Other ingredients)
If necessary, the resin varnish can contain other components such as additives as long as the effects of the present invention are not impaired. These may contain 1 type independently, and may contain 2 or more types.

(Additive)
Examples of the additive include a curing accelerator, a colorant, an antioxidant, a reducing agent, an ultraviolet absorber, a fluorescent whitening agent, an adhesion improver, and an organic filler. These may be used individually by 1 type and may use 2 or more types together.

(Organic solvent)
The resin varnish contains an organic solvent from the viewpoint of facilitating handling and from the viewpoint of facilitating manufacture of a prepreg described later.
The organic solvent is not particularly limited. For example, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol, Alcohol solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether solvents such as tetrahydrofuran ; Aromatic solvents such as toluene, xylene, mesitylene; Form Nitrogen-containing solvents including amide solvents such as amide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; sulfur atoms including sulfoxide solvents such as dimethyl sulfoxide Solvent; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, propylene glycol monomethyl ether acetate, ethyl acetate and the like.
Among these, from the viewpoint of solubility, alcohol solvents, ketone solvents, and nitrogen atom-containing solvents are preferable, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl cellosolve, and propylene glycol monomethyl ether are more preferable, and methyl ethyl ketone and methyl isobutyl ketone are preferable. More preferred is methyl ethyl ketone.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent in the resin varnish may be appropriately adjusted to such an extent that the resin varnish can be easily handled, and is not particularly limited as long as the coating property of the resin varnish is good. The concentration (concentration of components other than the organic solvent) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass, and even more preferably 50 to 80% by mass.

[Prepreg]
The prepreg of the present invention contains the resin varnish of the present invention, and the production method is not particularly limited. For example, the resin varnish is impregnated or coated on a sheet-like reinforcing substrate, and heated. Semi-cured (B-stage) can be produced.
As the prepreg sheet-like reinforcing substrate, known materials used for various types of laminates for electrical insulating materials can be used. As the material of the sheet-like reinforcing base material, natural fibers such as paper and cotton linter; inorganic fibers such as glass fiber and asbestos; organic fibers such as aramid, polyimide, polyvinyl alcohol, polyester, tetrafluoroethylene, and acrylic; A mixture etc. are mentioned. Among these, glass fiber is preferable from the viewpoint of flame retardancy. Examples of the glass fiber substrate include a woven fabric using E glass, C glass, D glass, S glass, or the like, a glass woven fabric obtained by bonding short fibers with an organic binder; a mixture of glass fibers and cellulose fibers, and the like. It is done. More preferably, it is a glass woven fabric using E glass.
These sheet-like reinforcement base materials have shapes, such as a woven fabric, a nonwoven fabric, a robink, a chopped strand mat, or a surfacing mat, for example. In addition, a material and a shape are selected by the use and performance of the target molding, and 1 type may be used independently and 2 or more types of materials and shapes can also be combined as needed.
The thickness of the prepreg of the present invention is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm, and more preferably 0.05 to 0.2 mm from the viewpoint of enabling moldability and high-density wiring. Is more preferable.

The prepreg of the present invention thus obtained can have a standard deviation σ determined according to the following method of 0.012% or less. This means that the variation in the dimensional change amount is small.
(Calculation method of standard deviation σ)
A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate with respect to the initial value of each measurement distance, and a standard deviation σ with respect to the average value is calculated.
The image measuring machine is not particularly limited, but for example, “QV-A808P1L-D” (manufactured by Mitutoyo) can be used.

The standard deviation σ is preferably 0.011% or less, more preferably 0.010% or less, and further preferably 0.009% or less. The lower limit value of the standard deviation σ is not particularly limited, but is usually 0.003% or more, 0.005% or more, 0.006% or more, 0.007 % Or more.

[Laminated board]
The laminated board of this invention contains the said prepreg and metal foil. For example, it can be manufactured by using one sheet of the prepreg or stacking 2 to 20 sheets as necessary, and arranging metal foil on one side or both sides thereof, preferably by heating and laminate molding. In addition, the laminated board which has arrange | positioned metal foil may be called a metal-clad laminated board.
The metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, preferably copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is preferable, copper and amylnium are more preferable, and copper is more preferable.
As the molding conditions of the laminated plate, a known molding method of a laminated plate for an electrical insulating material and a multilayer plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. Molding can be performed at 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.
Moreover, the prepreg of the present invention and the printed wiring board for inner layer can be combined and laminated to produce a multilayer board.
There is no restriction | limiting in particular in the thickness of metal foil, According to the use etc. of a printed wiring board, it can select suitably. The thickness of the metal foil is preferably 0.5 to 150 μm, more preferably 1 to 100 μm, still more preferably 5 to 50 μm, and particularly preferably 5 to 30 μm.

In addition, it is also preferable to form a plating layer by plating metal foil.
The metal of the plating layer is not particularly limited as long as it can be used for plating. The metal of the plating layer is preferably made of copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron, titanium, chromium, and an alloy containing at least one of these metal elements. Preferably it is selected.
There is no restriction | limiting in particular as a plating method, For example, a well-known method, for example, the electroplating method and the electroless-plating method, can be utilized.

[Printed wiring board]
The present invention also provides a printed wiring board comprising the prepreg or the laminated board.
The printed wiring board of the present invention can be produced by subjecting a metal foil of a metal-clad laminate to circuit processing. For example, after forming a resist pattern on the surface of the metal foil, the unnecessary portion of the metal foil is removed by etching, the resist pattern is peeled off, a necessary through hole is formed by a drill, and a resist pattern is formed again. It can be performed by plating for conducting through holes and finally peeling off the resist pattern. The above-described metal-clad laminate is further laminated on the surface of the printed wiring board thus obtained under the same conditions as described above, and further, the circuit is processed in the same manner as described above to obtain a multilayer printed wiring board. Can do. In this case, it is not always necessary to form a through hole, a via hole may be formed, and both can be formed. Such multi-layering is performed as many times as necessary.

[Semiconductor package]
The semiconductor package of the present invention is obtained by mounting a semiconductor on the printed wiring board of the present invention. The semiconductor package of the present invention can be manufactured by mounting a semiconductor chip, a memory or the like at a predetermined position of the printed wiring board of the present invention.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention in any way. Using the thermosetting resin composition according to the present invention, a resin varnish, a prepreg produced using the resin varnish, and a copper-clad laminate were produced, and each evaluation was performed according to the following methods.

[Evaluation methods]
<1. Heat resistance (Reflow soldering heat resistance)>
Using the four-layer copper-clad laminate produced in each example, the maximum temperature reached 266 ° C., and flowing the four-layer copper-clad laminate for 30 seconds in a thermostatic bath environment of 260 ° C. or higher was regarded as one cycle. Thus, the number of cycles until it was confirmed that the substrate was swollen was obtained. It can be said that the greater the number of cycles, the better the heat resistance, and the sufficient heat resistance is 10 cycles or more.

<2. Relative permittivity (Dk)>
Using a network analyzer “8722C” (manufactured by Hewlett-Packard Company), the relative dielectric constant of the double-sided copper-clad laminate at 1 GHz was measured by a triplate structure linear line resonator method. The test piece size is 200 mm x 50 mm x thickness 0.8 mm. A straight line (line length 200 mm) with a width of 1.0 mm is formed by etching at the center of one side of one double-sided copper-clad laminate, and the back side is A ground layer was formed by leaving copper on the entire surface. For the other double-sided copper-clad laminate, one side was etched entirely and the back side was a ground layer. These two double-sided copper-clad laminates were stacked with the ground layer on the outside to form a strip line. The measurement was performed at 25 ° C.
The smaller the relative dielectric constant, the better.

<3. Metal foil adhesion (copper foil peel strength)>
Metal foil adhesion was evaluated by copper foil peel strength. The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “ammonium persulfate (APS)” (manufactured by ADEKA) to form a copper foil having a width of 3 mm to produce an evaluation board. The peel strength of the copper foil was measured using “AG-100C” (manufactured by Shimadzu Corporation). It shows that it is excellent in metal foil adhesiveness, so that a value is large.

<4. Glass transition temperature (Tg)>
The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation substrate from which the copper foil was removed. Q400EM "(manufactured by TA Instruments) was used to observe the thermal expansion characteristics at 30 to 260 ° C. in the plane direction (Z direction) of the evaluation substrate, and the inflection point of the expansion amount was defined as the glass transition temperature.

<5. Low thermal expansion>
The double-sided copper-clad laminate produced in each example was immersed in a copper etching solution “Ammonium Persulfate (APS)” (manufactured by ADEKA Corporation) to produce a 5 mm square evaluation substrate from which the copper foil was removed. The thermal expansion coefficient (linear expansion coefficient) in the surface direction of the evaluation substrate was measured using “Q400EM” (manufactured by TA Instruments). In order to remove the influence of the thermal strain of the sample, the temperature rising / cooling cycle was repeated twice, and the coefficient of thermal expansion [ppm / ° C.] of 30 ° C. to 260 ° C. in the second temperature displacement chart was measured. An index of low thermal expansion was used. The smaller the value, the better the low thermal expansion. In the table, the thermal expansion coefficient below Tg (denoted as “<Tg”) and the thermal expansion coefficient above Tg (denoted as “> Tg”) are shown separately.
Measurement conditions 1 ^st Run: room temperature → 210 ° C. (temperature increase rate 10 ° C./min)
2 ^nd Run: 0 ° C. → 270 ° C. (temperature increase rate 10 ° C./min)
The copper-clad laminate is desired to be further reduced in thickness, and in conjunction with this, the prepreg constituting the copper-clad laminate is also being considered to be thinner. Since the thinned prepreg is likely to warp, it is desired that the prepreg warp during heat treatment be small. In order to reduce the warpage, it is effective that the coefficient of thermal expansion in the surface direction of the substrate is small.

<6. Plating rotation (Laser workability)>
Using the laser machine “LC-2F21B / 2C” (manufactured by Hitachi Via Mechanics Co., Ltd.) with the target hole diameter of 80 μm, Gaussian, and cycle mode for the 4-layer copper-clad laminate produced in each example, the copper direct method The laser was drilled with a pulse width of 15 μs × 1 and 7 μs × 4.
Regarding the obtained laser drilled substrate, the swelling liquid “Swelling Dip Securigant P” (manufactured by Atotech Japan Co., Ltd.) is 70 ° C. for 5 minutes, and the roughening liquid “Dosing Securigant P500J” (manufactured by Atotech Japan Co., Ltd.) is used. The desmear treatment was carried out at 70 ° C. for 9 minutes using the neutralizing solution “Reduction Conditioner Securigant P500” (manufactured by Atotech Japan Co., Ltd.) at 40 ° C. for 5 minutes. Thereafter, the electroless plating solution “Prigant MSK-DK” (manufactured by Atotech Japan Co., Ltd.) at 30 ° C. for 20 minutes, and the electroplating solution “Kaparaside HL” (manufactured by Atotech Japan Co., Ltd.) at 24 ° C., 2 A / dm ² , After 2 hours, the laser-processed substrate was plated.
The cross section of the obtained laser drilled substrate was observed, and the plating coverage was confirmed. As a method for evaluating the throwing power of plating, the difference between the plating thickness at the top of the laser hole and the plating thickness at the bottom of the laser hole is preferably within 10% of the plating thickness at the top of the laser hole. The existence ratio (%) of holes included in this range in the hole was determined.

<7. Formability>
For the four-layer copper-clad laminate produced in each example, after removing the outer layer copper, the presence or absence of voids and blurring in the in-plane of 340 mm × 500 mm was visually confirmed as resin embedding ability, and an index of formability It was. When there is no void or blur, it is indicated as “good”, and when there is a void or blur, this is indicated. When there is no void and blur, it can be said that the moldability is good.

<8. Evaluation of variation in dimensional change>
About the double-sided copper clad laminated board produced in each example, the hole with a diameter of 1.0 mm was implemented in the surface as FIG. As shown in FIG. 1, the distance between three points in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) of the glass cloth is shown in the image. Measurement was performed using a measuring instrument “QV-A808P1L-D” (manufactured by Mitutoyo), and each measurement distance was set as an initial value. Thereafter, the outer layer copper foil was removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) The distance was measured. The average value of the rate of change is calculated from the rate of change of each measurement distance relative to the initial value [(measured value−initial value) × 100 / initial value], and the standard deviation σ is calculated for the average value. It was used as an index of variation in dimensional change. A small value of the standard deviation σ indicates that the variation in dimensional change is small and preferable.

Hereinafter, each component used in Examples and Comparative Examples will be described.

Component (A): Solutions of maleimide compounds (A-1) to (A-5) produced in the following Production Examples A-1 to A-5 were used.
[Production Example A-1]
In a 1 L capacity reaction vessel equipped with a thermometer, a stirrer and a moisture meter with a reflux condenser, 12.1 g of 4,4′-diaminodiphenylmethane, 174.4 g of bis (4-maleimidophenyl) methane, p-aminophenol 13.3 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C. for 2 hours to obtain a dimethylacetamide solution of maleimide compound (A-1) (Mw = 965) having an acidic substituent and an N-substituted maleimide group. This was used as component (A-1).

[Production Example A-2]
In a 1 L reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 22.8 g of 4,4′-diaminodiphenylmethane, 164.5 g of bis (4-maleimidophenyl) methane, p-aminophenol 12.5 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C. for 2 hours to give a dimethylacetamide of maleimide compound (A-2) (Mw = 1,021) having an acidic substituent and an N-substituted maleimide group A solution was obtained and used as component (A-2).

[Production Example A-3]
In a reaction vessel having a volume of 1 L equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 6.2 g of 4,4′-diaminodiphenylmethane, 179.8 g of bis (4-maleimidophenyl) methane, p-aminophenol 13.7 g and 330.0 g of dimethylacetamide were added and reacted at 100 ° C. for 2 hours to obtain a dimethylacetamide solution of maleimide compound (A-3) (Mw = 908) having an acidic substituent and an N-substituted maleimide group. This was used as component (A-3).

[Production Example A-4]
In a reaction vessel having a volume of 1 L equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 18.2 g of 4,4′-diaminodiphenylmethane, 174.9 g of bis (4-maleimidophenyl) methane, p-aminophenol 6.7 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C. for 2 hours to give a dimethylacetamide of maleimide compound (A-4) (Mw = 1,034) having an acidic substituent and an N-substituted maleimide group. A solution was obtained and used as component (A-4).

[Production Example A-5]
In a reaction vessel having a volume of 1 L equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, 4.9 g of 4,4′-diaminodiphenylmethane, 178.5 g of bis (4-maleimidophenyl) methane, p-aminophenol 16.3 g and dimethylacetamide 330.0 g were added and reacted at 100 ° C. for 2 hours to obtain a dimethylacetamide solution of maleimide compound (A-5) (Mw = 911) having an acidic substituent and an N-substituted maleimide group. This was used as component (A-5).

In addition, the weight average molecular weight (Mw) of the maleimide compound obtained by the said manufacture example was converted from the calibration curve using a standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSK standard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation] Was approximated by a cubic equation. The GPC conditions are shown below.
Apparatus: (Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]),
(Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]),
(Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation])
Column: TSKgel SuperHZ2000 + TSKgel SuperHZ2300 (all manufactured by Tosoh Corporation)
Column size: 6.0 mm × 40 mm (guard column), 7.8 mm × 300 mm (column)
Eluent: Tetrahydrofuran Sample concentration: 20mg / 5mL
Injection volume: 10 μL
Flow rate: 0.5 mL / min Measurement temperature: 40 ° C

Component (B): Cresol novolac type epoxy resin “EPICLON (registered trademark) N-673” (manufactured by DIC Corporation)
Component (C-1): “SMA (registered trademark) EF40” (styrene / maleic anhydride = 4, Mw = 11,000, manufactured by CRAY VALLEY)
Component (C-2): “SMA (registered trademark) 3000” (styrene / maleic anhydride = 2, Mw = 7,500, manufactured by CRAY VALLEY)
Component (C-3): “SMA (registered trademark) EF80” (styrene / maleic anhydride = 8, Mw = 14,400, manufactured by CRAY VALLEY)
Component (C-4): “SMA (registered trademark) 1000” (styrene / maleic anhydride = 1, Mw = 5,000, manufactured by CRAY VALLEY)

Component (D): fused silica surface-treated with an aminosilane coupling agent (average particle size: 1.9 μm, specific surface area 5.8 m ² / g)

(E) Component: Dicyandiamide (F) Component: Aromatic phosphoric acid ester (see the structural formula below)

[Examples 1 to 15, Comparative Examples 1 and 2]
Each component shown above was blended as shown in the following Tables 1 to 4 (however, in the case of a solution, the amount in terms of solid content is indicated), and methyl ethyl ketone was further added so that the nonvolatile content of the solution was 67% by mass. A resin varnish was prepared.
Each of the obtained resin varnishes was impregnated with IPC standard # 3313 glass cloth (0.1 mm) and dried at 160 ° C. for 4 minutes to obtain a prepreg.

(Production and performance evaluation of double-sided copper-clad laminates)
Copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 18 μm is layered on both sides of the above-described eight prepregs, and the temperature is 190 ° C. and pressure is 25 kgf / cm ² (2.45 MPa). Heat-press molding for a minute to prepare a double-sided copper-clad laminate with a thickness of 0.8 mm (equivalent to 8 prepregs), and using the copper-clad laminate, according to the above methods, relative dielectric constant, metal foil adhesion, Glass transition temperature (Tg) and low thermal expansion were measured and evaluated.
Also, a 18 μm thick copper foil “3EC-VLP-18” (manufactured by Mitsui Kinzoku Co., Ltd.) is stacked on both sides of one prepreg, and heated for 90 minutes at a temperature of 190 ° C. and a pressure of 25 kgf / cm ² (2.45 MPa) A double-sided copper-clad laminate having a thickness of 0.1 mm (for one prepreg) was prepared, and the dimensional variation was measured and evaluated using the double-sided copper-clad laminate according to the above-described method.

(Production and performance evaluation of 4-layer copper-clad laminate)
On the other hand, one prepreg was used, and a copper foil “YGP-18” (manufactured by Nippon Electrolytic Co., Ltd.) having a thickness of 18 μm was stacked on both sides at a temperature of 190 ° C. and a pressure of 25 kgf / cm ² (2.45 MPa). After heat-press molding for 90 minutes to produce a double-sided copper-clad laminate with a thickness of 0.1 mm (one prepreg), inner layer adhesion treatment (“BF treatment solution” (manufactured by Hitachi Chemical Co., Ltd.) on both copper foil surfaces ), And prepregs with a thickness of 0.05 mm are stacked one by one, and a copper foil “YGP-18” (manufactured by Nippon Electrolytic Co., Ltd.) with a thickness of 18 μm is stacked on both sides, and the temperature is 190 ° C. and the pressure is 25 kgf / A four-layer copper-clad laminate was produced by heating and pressing at cm ² (2.45 MPa) for 90 minutes. Using the four-layer copper-clad laminate, heat resistance, plating-around property and formability were evaluated according to the above methods.
The results are shown in Tables 1 to 4.

From the above results, the following was found.
In Examples 1 to 15, the heat resistance of the reflow solder achieved 10 cycles or more, which is higher than the required heat resistance level, low dielectric constant, high metal foil adhesion and high glass transition temperature were obtained, and low thermal expansion was exhibited. . Moreover, it confirmed that it had the favorable revolving property with plating from having jumped out of the moderate glass cloth from a wall surface, and having an appropriate roughening shape. Also in the moldability, the embedding property of the resin was good, and abnormalities such as blurring and voids were not confirmed.
Further, in Examples 1 to 15, the standard deviation σ was small, and the variation in the dimensional change amount was sufficiently suppressed. On the other hand, in Comparative Examples 1 and 2, the standard deviation σ exceeded 0.012%, and the variation in the dimensional change amount became large.

The resin varnish obtained by the present invention, the prepreg comprising the resin varnish, and the laminate comprising the prepreg have high heat resistance, low relative dielectric constant, high metal foil adhesion, high glass transition temperature, low heat Since it has expansibility, is excellent in formability and plating-around properties, and has little variation in dimensional change, it is useful as a printed wiring board and a semiconductor package for electronic equipment.

Claims (15)

1. (A) a maleimide compound,
   (B) an epoxy resin, and (C) a copolymer resin having a structural unit derived from an aromatic vinyl compound and a structural unit derived from maleic anhydride,
   Containing
   The (A) maleimide compound is obtained by reacting (a1) a maleimide compound having at least two N-substituted maleimide groups, (a2) a monoamine compound and (a3) a diamine compound. A maleimide compound having a group,
   The (A) maleimide compound is reacted with the use ratio of the component (a2) to the component (a3) [component (a2) / component (a3)] (molar ratio) being 0.9 to 5.0. Resin varnish that can be obtained.
2. The resin varnish according to claim 1, wherein the (a2) monoamine compound is represented by the following general formula (a2-1), and the (a3) diamine compound is represented by the following general formula (a3-1).
   

   

   
   (In General Formula (a2-1), R ^A4 represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ^A5 represents an alkyl group having 1 to 5 carbon atoms or a halogen atom. t is an integer of 1 to 5, u is an integer of 0 to 4, and 1 ≦ t + u ≦ 5, provided that when t is an integer of 2 to 5, a plurality of R ^A4 may be the same And when u is an integer of 2 to 4, a plurality of R ^A5 may be the same or different.)
   

   

   
   (In the general formula (a3-1), X ^A2 represents an aliphatic hydrocarbon group having 1 to 3 carbon atoms or —O—. R ^A6 and R ^A7 each independently represents an alkyl having 1 to 5 carbon atoms. A group, a halogen atom, a hydroxyl group, a carboxy group, or a sulfonic acid group, and v and w are each independently an integer of 0 to 4.)
3. The resin according to claim 1 or 2, wherein the relationship between the sum of -NH ₂ group equivalents of the component (a2) and the component (a3) and the maleimide group equivalent of the component (a1) satisfies the following formula: varnish.
   0.1 ≦ [maleimide group equivalent] / [-NH ₂ group equivalent] ≦ 10
4. The component (B) is bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl novolak type epoxy resin and dicyclopentadiene. The resin varnish according to any one of claims 1 to 3, which is at least one selected from the group consisting of type epoxy resins.
5. The component (C) is a copolymer resin having a structural unit represented by the following general formula (Ci) and a structural unit represented by the following formula (C-ii): The resin varnish according to any one of the above items.
   

   

   
   (Wherein R ^C1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^C2 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 6 to 20 carbon atoms) An aryl group, a hydroxyl group, or a (meth) acryloyl group, where x is an integer of 0 to 3, provided that when x is 2 or 3, a plurality of R ^C2 may be the same or different. May be.)
6. In the component (C), the content ratio of the structural unit derived from the aromatic vinyl compound and the structural unit derived from maleic anhydride [the structural unit derived from the aromatic vinyl compound / the structural unit derived from maleic anhydride] (mole The resin varnish according to any one of claims 1 to 4, wherein the ratio) is 1 to 9.
7. The content of the components (A) to (C) is 15 to 65 parts by weight of component (A) and 15 to 65 parts of component (B) with respect to 100 parts by weight of the sum of the components (A) to (C). The resin varnish according to any one of claims 1 to 6, wherein the resin varnish is 50 parts by mass and the component (C) is 10 to 45 parts by mass.
8. The resin varnish according to any one of claims 1 to 7, further comprising (D) an inorganic filler.
9. The resin varnish according to any one of claims 1 to 8, further comprising (E) a curing agent.
10. The resin varnish according to any one of claims 1 to 9, further comprising (F) a flame retardant.
11. A prepreg comprising the resin varnish according to any one of claims 1 to 10.
12. The prepreg according to claim 11, wherein the standard deviation σ obtained according to the following method is 0.012% or less.
    Standard deviation σ calculation method:
    A copper foil having a thickness of 18 μm is stacked on both surfaces of one prepreg, and heat-press molding is performed at 190 ° C. and 2.45 MPa for 90 minutes, thereby producing a double-sided copper-clad laminate having a thickness of 0.1 mm. With respect to the double-sided copper clad laminate thus obtained, a hole having a diameter of 1.0 mm is formed in the plane at the locations 1 to 8 shown in FIG. Use an image measuring machine to determine the distance between each of the three points in the warp direction (1-7, 2-6, 3-5) and weft direction (1-3, 8-4, 7-5) shown in FIG. And measure each distance as the initial value. Thereafter, the outer layer copper foil is removed and heated at 185 ° C. for 60 minutes in a dryer. After cooling, in the same manner as the initial value measurement method, three points each in the warp direction (1-7, 2-6, 3-5) and the weft direction (1-3, 8-4, 7-5) Measure distance. An average value of the change rates is obtained from the change rate with respect to the initial value of each measurement distance, and a standard deviation σ with respect to the average value is calculated.
13. A laminate comprising the prepreg according to claim 11 or 12 and a metal foil.
14. A printed wiring board comprising the prepreg according to claim 11 or 12 or the laminate according to claim 13.
15. A semiconductor package comprising a semiconductor element mounted on the printed wiring board according to claim 14.

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