JP2000071411A - Resin-laminated substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin-laminated substrate which shows the good matching of the coefficients of linear thermal expansion in each direction and high head resistance or the like by using a prepreg which is obtained by compounding a specific heat-curable powderlike phenol resin and a polyfunctional amine-type epoxy resin with a specific derivative or the like and impregnating a base material with this compound. SOLUTION: A prepreg obtained by impregnating a base material with a heat-curable resin composition containing 0.1-10 pts.wt. imidazole silane derivative of formula I for 100 pts.wt. resin component obtained by compounding (I) 100 pts.wt. powderlike phenol resin with 25-400 pts.wt. polyfunctional amine- type epoxy resin with (II) 3 pieces or more of glycidyl group, is used and thermally pressed. (In the formula, R1 and R2 are each hydrogen or an alkyl group; R3 and R4 are each an alkyl group; n is an integer; and m is 1, 2 or 3). The phenol resin has such properties that the weight-average molecular weight in terms of polystyrene as a GPC measurement value is 1,000 or more and the free phenol content as a liquid chromatography measurement value is 500 ppm or less and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate substrate for a printed wiring board used in electronic equipment and the like, and particularly to a resin having a low coefficient of linear expansion, excellent heat resistance, and having resistance to migration and CAF. The present invention relates to a resin laminate excellent in characteristics and suitable as a material for a substrate for a semiconductor package such as a multichip module.

[0002]

2. Description of the Related Art In recent years, as electronic devices such as mobile communication devices have been rapidly reduced in size, and the mounting density of electronic components such as semiconductor packages has increased dramatically, further densification has been required. As a purpose, for example, in a multichip module, a method of directly bonding a semiconductor chip such as an LSI to a printed wiring board has been widely used. When the semiconductor chip is directly bonded to the printed wiring board in this manner, the linear expansion coefficient of the printed wiring board is reduced by 10% in terms of the linear expansion coefficient of the semiconductor chip (10
ppm / ° C. or less), and in the case of a package form such as a multi-chip module, heat resistance of 200 ° C. or more is required as in a normal semiconductor package. Recently, a resin laminate substrate formed by impregnating a glass fiber with a resin and forming a composite has been used as a printed wiring board. As this resin, an epoxy resin, a polyimide resin, a polyphenylene oxide (PPO) resin, a fluororesin, or the like is used. Further, as the glass fiber, (A) E glass (main component: 52 to 56 mol% of SiO ₂ (hereinafter simply referred to as “%
_{Called), Al 2 O 3 12~16%} , CaO 15~2
5%, 0~6% MgO, B 2 O 3 8~13%, (N
_{2 O + K 2 O) 0~1} %), for applications such as high strength is required (B) T glass or S-glass (main component: Si
O ₂ to about _{65%, Al 2 O 3 23~25} %, MgO
10-11%, ZrO ₂ 1% or less). Further, in order to increase the adhesion at the interface between the glass fiber and the resin, the surface of the glass fiber is generally subjected to a surface treatment with a coupling agent such as a silane coupling agent. On the other hand, characteristics required for a resin laminated substrate used for a printed wiring board include heat resistance, linear expansion coefficient,
Migration resistance, CAF (Conductive)
eAnodic Filamentity is particularly important.

However, as a printed wiring board made of resin, matching of the coefficient of linear expansion in the plane direction with the semiconductor chip (10 ppm / ° C. or less) and the coefficient of linear expansion in the thickness direction of the substrate for securing the reliability of the through-hole. Satisfactory in terms of matching of the coefficient of linear expansion (about 30 ppm / ° C) with the copper plating in the through hole, heat resistance (glass transition temperature Tg: 200 ° C or more) that can withstand several times of soldering, and cost At present there is nothing. Migration is a phenomenon in which copper of a circuit pattern formed on a substrate surface grows in a heated, humidified, and charged atmosphere, and causes a short circuit between adjacent patterns. As the migration resistance, for example, temperature 85 ° C.-humidity 85% -voltage 50
Under the condition of V, it is required that the short circuit does not occur for 1000 hours or more and the insulation resistance is 1 × 10 ⁸ Ω or more. In addition, CAF (Conductive)
Anodic Filament is a filamentous copper growth between the surface of the substrate on which the through-holes are formed and the through-holes, and causes a short circuit. The CAF resistance can be tested and evaluated under the same experimental conditions and criteria as the migration resistance. However, the effect of providing the through holes on the substrate also appears, so that the CAF resistance is much more severe than the migration resistance. There has been a strong demand for a resin laminated substrate that satisfies the migration resistance and the CAF resistance in addition to the heat resistance and the low linear expansion coefficient. Among the resins used in the above-mentioned conventional resin laminated substrate, epoxy resin has insufficient heat resistance, flame retardancy, and linear expansion coefficient, and polyimide resin and PPO resin have chemical resistance (especially polyimide resin has resistance to heat). (Alkaline property), which is not practical level. Fluororesin is difficult to process, and all of the resins (1) to (4) have high costs and insufficient migration resistance and CAF resistance.

In order to solve these problems, the present inventors have studied the use of a powdery phenolic resin for the resin of the resin laminated substrate, but this resin has characteristics such as heat resistance and low linear expansion coefficient. However, it was found that migration resistance and CAF resistance were still insufficient due to the presence of a hydroxyl group (-OH group) in the molecular structure. The present inventors have further studied and, as a result, blended a specific polyfunctional amine-type epoxy resin having three or more glycidyl groups with the powdery phenolic resin, to reduce the hydroxyl groups in the powdery phenolic resin. By reforming, the migration resistance has been successfully improved (Japanese Patent Application No. 10-174968). However, the CAF resistance, which is stricter than the migration resistance, has not been sufficiently satisfied, although the above resin blend has greatly improved.

[0005] The glass fiber used as the base material of the laminated board is
Although this is a major factor in determining the coefficient of linear expansion of the resin laminated substrate, the (A) E glass used for general purposes has a large linear expansion coefficient by itself, and it is difficult to reduce the linear expansion coefficient of the resin laminated substrate. is there. Further, (B) T glass or S glass has high strength and low linear expansion coefficient, and can also reduce the linear expansion coefficient of the resin laminated substrate.
When drilling or the like for forming a through hole is performed on a resin laminated substrate, separation occurs at the glass fiber / resin interface, adversely affecting migration resistance and CAF resistance, and the cost is much higher than that of E glass. There is. Further, among the characteristics required for the resin laminated substrate,
The coefficient of linear expansion and CAF resistance can be improved to some extent by increasing the adhesion at the interface between the resin and the glass fiber. As the method, it is common to treat the surface of the glass fiber with a coupling agent such as a silane coupling agent. However, the optimal coupling agent differs depending on the resin, and even if the same coupling agent is used, there is a large difference in adhesion due to the difference in resin.In addition, appropriate selection is necessary. A resin laminate satisfying the linear expansion coefficient and CAF resistance could not be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has good matching of linear expansion coefficients in both the surface direction and the thickness direction, and has excellent heat resistance and migration resistance. In addition, it is an object of the present invention to provide a resin laminate substrate for a printed wiring board which is excellent in CAF resistance and low in cost.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have been made of a specific thermosetting powdery phenolic resin and a specific polyfunctional amine type epoxy resin. The above object is achieved by producing a resin laminate using a prepreg impregnated in a glass fiber cloth with a resin composition in which a predetermined amount of a specific imidazole silane derivative and / or a hydrotalcite compound is blended with a resin component. It has been found that the present invention has been completed.

That is, the present invention relates to the following (1), (2),
(3) The invention of (4) and (5) is provided. (1) A polyfunctional amine type epoxy resin (II) having three or more glycidyl groups per 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D):
With respect to 100 parts by weight of the resin component containing 5 to 400 parts by weight, the following formula (1)

[0009]

Embedded image

(Wherein, R ¹ and R ² each represent hydrogen or an alkyl group, R ³ and R ⁴ each represent an alkyl group, n represents an integer, and m represents 1, 2 or 3) The imidazole silane derivative represented by 0.1
A resin laminated substrate obtained by hot pressing using a prepreg obtained by impregnating a base material with a thermosetting resin composition containing from 10 to 10 parts by weight. (A) G. P. C. (Gel permeation chromatography), the weight average molecular weight in terms of polystyrene is 1,000 or more, (B) the free phenol content is 500 ppm or less, as measured by liquid chromatography, (C) phenol Is a condensate of phenols and formaldehyde, and (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (b) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol. (C) the trifunctional residue is bonded to a methylene group at one of the 2, 4 and 6 positions of the phenol and at least at another position is a methylol group and / or a methylene group And (d) an infrared absorption spectrum by the KBr tablet method of 1600 cm ⁻¹ (attributable to benzene). The absorption intensity of D ₁₆₀₀ , and the largest absorption intensity in the range of 990 to 1015 cm ^-1 (the absorption peak attributed to the methylol group) are D _{990-10 15} and 890 cm ^-1 (of the isolated hydrogen atom of the benzene nucleus). D ₈₉₀ , the absorption intensity of the absorption peak) is represented by D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7 Filled, and (D) particle size 0.1-100
Contains μm spherical primary particles and their secondary aggregates. (2) Polyfunctional amine epoxy resin (II) 2 having three or more glycidyl groups per 100 parts by weight of powdery phenolic resin (I) having the following characteristics (A) to (D):
With respect to 100 parts by weight of the resin component containing 5 to 400 parts by weight, the following formula (1)

[0011]

Embedded image

(Wherein, R ¹ and R ² each represent hydrogen or an alkyl group, R ³ and R ⁴ each represent an alkyl group, n represents an integer, and m represents 1, 2 or 3) The imidazole silane derivative represented by 0.1
10 to 10 parts by weight and the following formula (2) Mg _x Zn _y Al ₂ · (OH) _{2 (x + y + 2)} · (CO ₃ ) ₁ -z _{/ 2} · (CLO ₄ ) _z · mH ₂ O (2 (Where x, y, and z each represent a number that satisfies the following condition: 0 ≦ y / x <102 ≦ x + y <200 ≦ z ≦ 2, and m represents 0 or any positive number). The hydrotalcite compound represented by 0.1)
A resin-laminated substrate, which is heated and pressed using a prepreg obtained by impregnating a base material with a thermosetting resin composition containing 10 parts by weight. (A) G. P. C. (Gel permeation chromatography), the weight average molecular weight in terms of polystyrene is 1,000 or more, (B) the free phenol content is 500 ppm or less, as measured by liquid chromatography, (C) phenol Is a condensate of phenols and formaldehyde, and (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (b) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol. (C) the trifunctional residue is bonded to a methylene group at one of the 2, 4 and 6 positions of the phenol and at least at another position is a methylol group and / or a methylene group And (d) an infrared absorption spectrum by the KBr tablet method of 1600 cm ⁻¹ (attributable to benzene). The absorption intensities of D ₁₆₀₀ and 990 to 1015 cm ⁻¹ (the absorption peaks belonging to the methylol group) are D _990-1015 and 890 cm ⁻¹ (the absorption of the isolated hydrogen atom of the benzene nucleus). When the absorption intensity of (peak) is represented by D ₈₉₀ , the relationship of both formulas of D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7 is satisfied. And (D) particle size 0.1-100
Contains μm spherical primary particles and their secondary aggregates. (3) The base material is E glass (main component: SiO ₂ 52 to 56)
Mol% (hereinafter simply referred to as%), Al ₂ O ₃ 12 to 1
6%, CaO 15-25%, MgO 0-6%, B _{2
O 3 8~13%, (N 2} O + K 2 O) 0~1%) , characterized in that is made of fibers (1) or (2) a resin laminated substrate according to claim.

(4) 100 parts by weight of a powdery phenolic resin (I) having the following properties (A) to (D):
Resin component 10 containing 25 to 400 parts by weight of polyfunctional amine type epoxy resin (II) having at least two glycidyl groups
With respect to 0 parts by weight, the following formula (2) Mg _x Zn _y Al ₂ · (OH) _{2 (x + y + 2)} · (CO ₃ ) _{1-z / 2} · (CLO ₄ ) _z · mH ₂ O (2) (where x, y, and z each represent a number satisfying the following condition: 0 ≦ y / x <102 ≦ x + y <200 ≦ z ≦ 2. M is 0 or any positive number. Hydrotalcite compound represented by the formula (1):
A resin-laminated substrate, which is heated and pressed using a prepreg obtained by impregnating a base material with a thermosetting resin composition containing 10 parts by weight. (A) G. P. C. (Gel permeation chromatography), the weight average molecular weight in terms of polystyrene is 1,000 or more, (B) the free phenol content is 500 ppm or less, as measured by liquid chromatography, (C) phenol Is a condensate of phenols and formaldehyde, and (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (b) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol. (C) the trifunctional residue is bonded to a methylene group at one of the 2, 4 and 6 positions of the phenol and at least at another position is a methylol group and / or a methylene group And (d) an infrared absorption spectrum by the KBr tablet method of 1600 cm ⁻¹ (attributable to benzene). The absorption intensities of D ₁₆₀₀ and 990 to 1015 cm ⁻¹ (the absorption peaks belonging to the methylol group) are D _990-1015 and 890 cm ⁻¹ (the absorption of the isolated hydrogen atom of the benzene nucleus). When the absorption intensity of (peak) is represented by D ₈₉₀ , the relationship of both formulas of D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7 is satisfied. And (D) particle size 0.1-100
Contains μm spherical primary particles and their secondary aggregates. (5) The polyfunctional amine type epoxy resin (II) is an aromatic glycidylamine type polyfunctional epoxy resin obtained from a reaction between an aromatic amine and epichlorohydrin, (1), (2), The resin laminated substrate according to (3) or (4). Here, the resin laminated substrate of the present invention refers to a laminate of a plurality of prepregs heated and pressurized, a laminate of a plurality of prepregs heated and pressurized and a copper foil layer formed on at least one surface thereof, And a copper foil layer formed on at least one surface of the prepreg by heating and pressing.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, each component of the resin composition used in the present invention will be described. (I) Powdery phenolic resin In the present invention, a powdery phenolic resin having the above-mentioned characteristics (A) to (D) is used. The weight average molecular weight defined in the above (A) is preferably 3,000 or more,
The upper limit is not particularly limited, but is usually about 12,000.
The free phenol content defined in the above (B) is preferably 300 ppm or less, and the lower limit is not particularly limited, but is usually 50 ppm or more.

As defined in (C) above, the powdered phenolic resin is a condensate of phenols and formaldehyde, and contains phenol or phenol containing at least 50% by weight, especially at least 70% by weight of phenol, For example, o-cresol, m-cresol, p-
Cresol, bis-phenol A, o-, m- or p-
It includes a condensate of formaldehyde with a mixture of one or more known phenol derivatives such as alkyl (preferably alkyl having 2 to 4 carbon atoms) phenol, p-phenylphenol, xylenol and resorcinol. The powdery phenolic resin used in the present invention comprises the three main bonding units of methylene group, methylol group, and trifunctional residue of phenol as defined in (C) and (B) above, as described in (C) ( (C) and (d) so as to satisfy the relationship. Here, the trifunctional residue of phenols means a residue having at least two bonds in addition to a phenolic hydroxyl group derived from phenol or the phenol derivative. Here, (C) (d)
The absorption intensity in the infrared absorption spectrum defined by is determined as follows.

Measurement of infrared absorption spectrum and absorption intensity
(Refer to FIG. 1 in the accompanying drawings) First, an infrared absorption spectrum is measured for a measurement sample prepared by a normal KBr tablet method using an infrared spectrophotometer. Next, the absorption intensity at a specific wavelength is obtained as follows. A baseline is drawn at the peak for which the absorption intensity is to be determined in the measured infrared absorption spectrum. Represents the transmittance of the apex of the peak at t _p, the representative of the transmittance of the baseline at that wavelength at t _b,
The absorption intensity D at the specific wavelength is given by the following equation. D = log (t _b / t _p ) Accordingly, for example, the absorption intensity of the peak at 890 cm ⁻¹ and 16
The ratio of the peak at 00 cm ^-1 to the absorption intensity is given as the ratio (D ₈₉₀ / D ₁₆₀₀ ) of the respective absorption intensities determined by the above equation.

In a certain phenolic resin, the ratio of the absorption intensity in the infrared absorption spectrum D _990-1015 / D ₁₆₀₀ to D
₈₉₀ / or D ₁₆₀₀ takes any value is largely due to the number of methylol groups in the molecular structure (-CH ₂ OH). If the number of methylol groups is large, the reactivity is high, but the stability is poor. Therefore, as described below, the absorption intensity ratio may be in the range defined by (C) and (d) so that the methylol groups are appropriately contained. It is preferable from the viewpoint of productivity and workability. The powdery phenolic resin used in the present invention has an absorption intensity in the infrared absorption spectrum of D.
_990-1015 / D ₁₆₀₀ = 0.2 to 9.0, preferably 0.4 to 5.0, more preferably 0.4 to 3.0. Having such a value indicates that the molecule contains an appropriate amount of a reactive methylol group. If this value exceeds the upper limit of the above range, the curing speed of the resin is increased, the storage stability of the varnish is reduced, and the impregnation workability is reduced. On the other hand, D _990-1015 / D
_When the value of ₁₆₀₀ is less than the lower limit of the above range, the crosslinking density when the resin composition is cured decreases, and the coefficient of linear expansion and the heat resistance characteristics decrease. Similarly, the powdery phenol resin used in the present invention has an absorption intensity in the infrared absorption spectrum of D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7, preferably 0.07 to 0.5, and more preferably 0.07 to 0.5. Is 0.07 to 0.2. Having a value in such a range indicates that the ortho and para positions of the phenol skeleton in the resin are appropriately substituted by a methylene bond or a methylol group. If this value exceeds the upper limit of the above range, the crosslinking density when the resin composition is cured decreases, the linear expansion coefficient and heat resistance deteriorate, and if it is less than the lower limit of the above range, the varnish viscosity increases. And impregnating workability decreases, which is not preferable.

The particle diameter of the primary particles defined in the above (D) is preferably 0.5 to 40 μm. The powdery phenolic resin (I) having the characteristics defined in the above (A) to (D) used in the present invention is different from a general phenolic resin such as a novolak phenolic resin or a resol phenolic resin. It is. With respect to the powdery phenol resin used in the present invention, G.P. P. C. By is usually less than 1,000 polystyrene equivalent weight average molecular weight, and one both or either D _990-1015 / D ₁₆₀₀ and D ₈₉₀ / D ₁₆₀₀ for absorption intensity in the infrared absorption spectrum was defined in the present invention The value is lower than the lower limit of the range. Specifically, for a novolak type phenol resin, D ₈₉₀ / D
₁₆₀₀ <0.05, and D for resol type phenol resin
_990-1015 / D ₁₆₀₀ <0.2, both of which do not satisfy the numerical range specified in the present invention. This means that the powdery phenolic resin used in the present invention that satisfies the conditions specified for the above properties has a higher molecular weight and a lower methylene crosslink density than novolak resins and resol resins,
It shows that it contains a moderately reactive methylol group. Further, also in the production method, when the ratio of formaldehyde and phenol as raw materials is F / P, the novolak type phenol resin is F / P = 0.8 to 1.0 (that is, phenol excess) and the resol under a acidic atmosphere. Type phenolic resin is produced under an alkaline atmosphere with F / P = 1.0 to 2.0 (that is, excess formaldehyde), whereas the powdery phenolic resin (I) used in the present invention is used.
Is usually F / P≫2.0 (that is, a large excess of formaldehyde) and is produced in a strongly acidic atmosphere with a large excess of hydrochloric acid. In this regard, when a powdery phenolic resin is produced in a strongly acidic atmosphere containing a large excess of hydrochloric acid, chlorine is left in the obtained resin, and this residual chlorine causes deterioration of migration resistance and CAF resistance of the resin laminated substrate. It is thought that it becomes one of. Therefore, the powdery phenolic resin (I)
It is preferable to use a material from which such residual chlorine has been removed (preferably 100 ppm or less). In terms of the properties after curing, the powdery phenolic resin (I) used in the present invention is not too hard as compared with general novolak-type phenolic resins or resol-type phenolic resins, has a moderate elongation, An excellent property such as a small expansion coefficient and high heat resistance, for example, a glass transition temperature of 180 ° C. or more can be imparted to the resin laminated substrate. Powdery phenolic resin (I) used in the present invention
Can be produced by a conventional method, for example, by the method described in JP-A-58-113243. As a commercially available powdery phenolic resin that can be used in the present invention, for example, "Bell Pearl" (trade name) manufactured by Kanebo Co., Ltd. can be mentioned. In the present invention, the powdery phenolic resin (I) is used as a varnish, that is, dissolved in a solvent. If the powdered phenolic resin (I) is not dissolved, the resulting product (substrate) will have poor appearance due to undissolved components remaining on the surface. Therefore, as the solvent, a solvent having good solubility in the powdery phenolic resin (I) (for example, methyl ethyl ketone) is selected and used.

(II) Polyfunctional amine type epoxy resin In the present invention, a polyfunctional amine type epoxy resin having three or more glycidyl groups is used. The polyfunctional amine-type epoxy resin is preferably an aromatic glycidylamine-type polyfunctional epoxy resin obtained from a reaction of an aromatic amine such as diaminodiphenylmethane and meta-xylylenediamine with epichlorohydrin. Examples of the aromatic glycidylamine-type polyfunctional epoxy resin preferably used in the present invention include resins such as tetraglycidyldiaminodiphenylmethane, tetraglycidylmethaxylylenediamine, and triglycidylaminophenol. The reason that the resin blended with the powdered phenolic resin (I) is limited to the polyfunctional amine epoxy resin (II) having three or more glycidyl groups is that the resin other than the polyfunctional amine epoxy resin (II) This is because it is impossible to achieve both improvement of migration resistance and CAF resistance, and other characteristics such as heat resistance and low linear expansion coefficient. That is, the modification of the hydroxyl group (-OH) contained in the powdery phenolic resin (I), which is considered to be one of the causes of deteriorating migration resistance and CAF resistance in resins other than the resin (II). Although it is not possible, or even with an epoxy resin, for example, a bisphenol-A type epoxy resin or a novolak type epoxy resin is effective in improving migration resistance and CAF resistance, but has a high glass transition point and the like. It is difficult to obtain high heat resistance and low coefficient of linear expansion. The polyfunctional epoxy resin (II) used in the present invention can be produced by a conventional method. Examples of commercially available products that can be used in the present invention include “Epototo YH-434” (trade name) manufactured by Toto Kasei Co., Ltd. The polyfunctional amine epoxy resin (I) used in the present invention
The state of I) is usually liquid.

In the present invention, the powdery phenolic resin (I) and the polyfunctional amine type epoxy resin (II) having three or more glycidyl groups are used in a ratio of the resin (I) to the resin (II) by weight. 100/25 to 100/400 (% by weight)
80/20 to 20/80), preferably 100/33 to 100/100 (parts by weight: 75/25 by weight).
５０50/50) is used. The ratio of the resins (I) and (II) is 100 parts by weight.
If the ratio is more than / 25, that is, if the ratio of the powdery phenolic resin (I) is more than 80% by weight, the migration resistance is passed but the CAF resistance is insufficient. When the ratio is less than 100/400 in terms of parts by weight, that is, when the ratio of the powdery phenolic resin is less than 20% by weight, the heat resistance inherent to the powdery phenolic resin in the obtained resin laminated substrate is obtained. In addition, characteristics such as low linear expansion coefficient and flame retardancy are impaired.

Imidazole silane derivative In the present invention, a resin composition obtained by mixing a predetermined amount of the imidazole silane derivative represented by the above formula (1) with a resin component is used. Hereinafter, the imidazole silane derivative will be described. In the formula (1), R ¹ and R ² are
They may be the same or different and each represents a hydrogen or an alkyl group. R ³ and R ⁴ may be the same or different,
Each represents an alkyl group. n represents an integer, and more preferably n is 6. m is 1, 2 or 3. In the present invention, by using the imidazole silane derivative having the above specific structure, the coefficient of linear expansion of the obtained resin laminated substrate can be reduced, and the migration resistance and CAF resistance can be significantly improved. This mechanism is considered as follows. First, the silanol (—SiOR ³ ) group in the imidazole silane derivative binds to the glass fiber as the base material and / or the coupling agent coated on the surface of the glass fiber to increase the adhesion strength between the resin and the glass fiber. This reduces the coefficient of linear expansion and prevents water and water from entering the resin / glass fiber interface, which is one of the causes of migration and CAF. Separation between layers can be prevented, and growth at the interface of copper (copper plating on a wall surface of a through hole) can be suppressed. Further, the imidazole ring in the imidazole silane derivative is coordinated with the copper of the circuit pattern provided on the substrate, thereby suppressing the growth of copper, and
Adhesion strength between circuits can be increased. In the present invention, the amount of the imidazole silane derivative is 0.1 to 100 parts by weight of the resin component in the resin composition.
It is 10 parts by weight, preferably 0.5 to 5 parts by weight. If the amount of the imidazole silane derivative is less than 0.1 part by weight with respect to 100 parts by weight of the resin component, the effect of the present invention cannot be obtained. Conversely, if the amount exceeds 10 parts by weight, the derivative is added. Not only is the obtained effect not further improved, but also there is a fear that various properties based on the resin component are adversely affected. In the present invention, as an imidazole silane derivative, IS-3000 manufactured by Japan Energy Co., Ltd.
Commercial products such as (trade name) can be used.

Hydrotalcite Compound In the present invention, a resin composition comprising a predetermined amount of a hydrotalcite compound represented by the above formula (2) in place of or in addition to the imidazole silane derivative is added to the resin component. Is used. Hereinafter, the hydrotalcite compound will be described. Hydrotalcite compounds
Although the composition is not generally specified, basically, Mg _1-x Al
_x (OH) ₂ basic layer and (CO ₃ ) _{2 / x} · mH ₂
It is a compound having a laminated structure composed of an intermediate layer made of O, and the composition of the entire compound is represented by the formula (2).
By using the hydrotalcite compound, chlorine remaining in the powdery phenolic resin is captured, thereby suppressing the growth of copper from a circuit provided on the substrate,
It is considered that migration resistance and CAF resistance can be improved. In the present invention, the compounding amount of the hydrotalcite compound is 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the resin component in the resin composition. If the amount of the hydrotalcite compound is less than 0.1 part by weight based on 100 parts by weight of the resin component, the effect of the present invention cannot be obtained. Conversely, if the amount exceeds 10 parts by weight, the compound is added. Not only is the obtained effect not further improved, but also there is a fear that various properties based on the resin component are adversely affected. In the present invention, commercially available products such as Alkamizer-1 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd. can be used as the hydrotalcite compound. In the present invention, when the imidazole silane derivative and the hydrotalcite compound are used in combination, the compounding amounts of the respective compounds and the preferable ranges thereof are as described above.

In the resin-laminated substrate of the present invention, the substrate to be used is not particularly limited, but for example, glass fiber can be preferably used. Any glass fiber may be used as long as it is generally used for a substrate of a laminated substrate, but typical examples include E glass, high-strength T glass and S glass. It is also preferable to treat the surface of the glass fiber with a silane coupling agent or the like. In particular, the E-glass (chemical component: Si), in which the linear expansion coefficient of the glass material itself is not so small and it is difficult to obtain a low linear expansion coefficient as a base material of the laminated substrate.
O ₂ 52 to 56%, Al ₂ O ₃ 12 to 16%, Ca
O 15 to 25%, MgO 0 to 6%, B ₂ O ₃ 8 to
13%, (N ₂ O + K ₂ O) 0-1%)
The effect of the present invention for reducing the coefficient of linear expansion is particularly remarkable.
In addition to the resins (I) and (II), the imidazole silane derivative and the hydrotalcite compound, they are usually used in resin-laminated base materials such as flame retardants and coloring agents for the purpose of improving other properties. Can be added in a range that does not impair the purpose of the present invention. For example,
In order to improve the flame resistance of the laminated substrate in the present invention,
Halogen compounds such as brominated bisphenol A type epoxy resin, phosphorus compounds such as cresyl diphenyl phosphate, zinc borate, and inorganic flame retardants such as aluminum hydroxide;
Other flame retardants may be added to the resin composition.

Hereinafter, the production of the resin laminated substrate of the present invention from the thermosetting resin composition will be described. The steps of manufacturing a prepreg from a resin composition, curing by pressing, and after-curing can be performed according to a conventional method.
First, a thermosetting resin composition containing an imidazole silane derivative or a hydrotalcite compound in a resin component composed of the powdery phenolic resin (I) and the polyfunctional amine-type epoxy resin (II), for example, methyl ethyl ketone A varnish (resin solution) is obtained by dissolving in a suitable solvent having good solubility for each resin or compound such as. Alternatively, after dissolving the resin (I), the resin (II), the imidazole silane derivative, and the hydrotalcite compound in an appropriate solvent, the solution may be simply mixed, or the solvent may be further added and mixed. Next, the obtained varnish is impregnated into a substrate such as a glass fiber cloth such as an S glass cloth or an E glass cloth, and is preliminarily cured by removing the solvent by heating and drying to obtain a prepreg. The glass fiber cloth may be previously subjected to a surface treatment by a silane coupling treatment or the like. Next, one prepreg and a copper foil layer are laminated on at least one surface thereof, or two or more, preferably 2 to 4 prepregs are laminated, and if necessary, a copper foil layer is laminated on at least one surface thereof and heated. It is pressed and after-cured to obtain the resin laminated substrate of the present invention. Although the thickness of the resin laminated substrate of the present invention is not particularly limited, it is generally 0.05 to 1.5 mm.

[0025]

The present invention will be described below in more detail with reference to examples and comparative examples.

Example 1 50 parts by weight of a powdery phenolic resin [trade name: Bellpearl S890 manufactured by Kanebo Co., Ltd.] and tetraglycidyl diaminodiphenylmethane resin [trade name: Epototo YH-434 manufactured by Toto Kasei Co., Ltd., epoxy equivalent 110-14
0 g / eq] of 50 parts by weight, and a resin composition consisting of 3 parts by weight of an imidazole silane derivative [trade name: IS-3000 manufactured by Japan Energy Co., Ltd.] was dissolved in 100 parts by weight of methyl ethyl ketone to obtain a varnish. .
This varnish was impregnated with E glass fiber having a thickness of 0.18 mm, and then dried in a thermostat at 100 ° C. to prepare a prepreg. Next, one obtained by laminating three prepregs
A resin laminated substrate having a thickness of 0.6 mm was formed by heating and pressing with a press at 80 ° C. The following characteristics were tested on the obtained resin laminated substrate. (1) Coefficient of linear expansion Using the obtained resin-laminated substrate, the TMA method (Thermo-Mechani) described in JIS C6481 is used.
cal-Analysis method), the linear expansion coefficient of each of the sample substrate in the plane direction and the thickness direction was measured. Coefficient of linear expansion in the plane direction of less than 15 ppm / ° C, 6 in the thickness direction
If it is less than 5 ppm / ° C., it is practically no problem level. However, if it exceeds these, problems such as cracks may occur during heating. (2) Glass transition temperature The obtained resin laminated substrate was measured by the TMA method according to JIS C4681. From the point of heat resistance, 200 ° C or more is accepted, and less than 200 ° C is rejected. (3) Migration resistance Separately from the resin laminated substrate, a copper foil having a thickness of 0.6 mm is placed on both surfaces of a laminate of the three prepregs, and a copper foil having a thickness of 12 μm is placed on both surfaces. A substrate was created. A comb-shaped copper circuit having a line / space of 0.1 mm / 0.1 mm was formed on the surface of the laminated substrate by an etching method.
The migration resistance was tested under the condition of 0V. A pass is made when no short circuit occurs between adjacent copper circuits due to copper growth for 1000 hours, that is, when insulation resistance of 1 × 10 ⁹ Ω or more is maintained for 1000 hours or more. Those failing this test are indicated by the time (hour) until a short circuit occurs. (4) CAF resistance A through-hole having a diameter of 0.3 mm was formed on a copper-clad laminate prepared in the same manner as in (3) above with a through-hole interval of 0.1 mm.
6mm, after copper plating on the hole wall,
Line / space = 0.
A copper circuit of 2 mm / 0.6 mm was formed, and the CAF resistance was tested under the conditions of a temperature of 85 ° C., a humidity of 85%, and a charged AC of 50 V. A short circuit between adjacent copper circuits due to the growth of copper does not occur for 1000 hours or more, that is, an insulation resistance of 1 × 10 ⁸ Ω or more is maintained for 1000 hours or more. Those failing this test are indicated by the time (hour) until a short circuit occurs.

Example 2 The same procedure as in Example 1 was repeated except that the resin component of the resin composition was 75 parts by weight of the same powdery phenolic resin as in Example 1 and 25 parts by weight of tetraglycidyldiaminodiphenylmethane resin. A copper-clad laminate was prepared and tested in the same manner as in Example 1. Example 3 The same procedure as in Example 1 was repeated except that the resin component of the resin composition was 25 parts by weight of a powdery phenolic resin and 75 parts by weight of a tetraglycidyldiaminodiphenylmethane resin as in Example 1. A substrate was prepared, and a test was performed in the same manner as in Example 1. Example 4 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 1 except that the glass fiber impregnated with varnish was changed to S-glass fiber having a thickness of 0.18 mm, and tested in the same manner as in Example 1. Was done.

The same powdery phenolic resin 90 parts by weight of a resin component in Example 1 of Comparative Example 1 resin composition, except that a tetraglycidyl diaminodiphenylmethane resins 10 parts by weight layered substrate in the same manner as in Example 1 and A copper-clad laminate was prepared and tested in the same manner as in Example 1. Comparative Example 2 The same procedure as in Example 1 was repeated except that the resin components of the resin composition were 10 parts by weight of the powdery phenolic resin and 90 parts by weight of the tetraglycidyldiaminodiphenylmethane resin as in Example 1. A substrate was prepared, and a test was performed in the same manner as in Example 1. Comparative Example 3 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 1 except that the imidazolesilane derivative was not added, and a test was performed in the same manner as in Example 1. Comparative Example 4 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 2 except that the imidazole silane derivative was not added, and a test was performed in the same manner as in Example 1. Comparative Example 5 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 3 except that the imidazolesilane derivative was not added, and a test was conducted in the same manner as in Example 1.

Comparative Example 6 The resin component of the resin composition was a novolak-type phenol resin (trade name: Shownol BRG-55 manufactured by Showa Polymer Co., Ltd.).
6) A laminated board and a copper-clad laminated board were prepared in the same manner as in Example 1 except that 50 parts by weight of tetraglycidyldiaminodiphenylmethane resin was used, and the test was conducted in the same manner as in Example 1. Was done. Comparative Example 7 Except that the resin component of the resin composition was 50 parts by weight of the same powdery phenolic resin as in Example 1, and 50 parts by weight of bisphenol A / epichlorohydrin type epoxy resin (trade name: Epotote YD128 manufactured by Toto Kasei Co., Ltd.) A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 1, and a test was performed in the same manner as in Example 1. Comparative Example 8 The resin component of the resin composition was the same as in Example 1 except that 50 parts by weight of a powdery phenolic resin and a phenol novolak epoxy resin (trade name: Epototo YDPN63 manufactured by Toto Kasei Co., Ltd.)
8) A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 1 except that the amount was 50 parts by weight, and a test was performed in the same manner as in Example 1. Tables 1 and 2 show the compositions and base materials of the resin compositions used in the examples and comparative examples, and the results of the property tests.
Shown in

[0030]

[Table 1]

[0031]

[Table 2]

Examples 1 to 4 and Comparative Example 1 shown in Tables 1 and 2
As is clear from the comparison of the results of Comparative Examples Nos. To 8, imidazole was added to the resin component of the specific powdery phenolic resin and the polyfunctional amine type epoxy resin having three or more glycidyl groups in the thermosetting resin laminated substrate. By using a resin composition to which a predetermined amount of a silane derivative was added, migration resistance and CAF resistance could be significantly improved, and the linear expansion coefficient could be reduced.

Example 5 A laminated substrate was prepared in the same manner as in Example 1 except that 4 parts by weight of a hydrotalcite compound [trade name: Alkamizer-1 manufactured by Kyowa Chemical Industry Co., Ltd.] was used instead of 3 parts by weight of the imidazole silane derivative. And a copper-clad laminated board were prepared, and
Each property was tested in the same manner as described above. Example 6 The same procedure as in Example 5 was repeated except that the resin component of the resin composition was 75 parts by weight of the same powdery phenolic resin and 25 parts by weight of tetraglycidyldiaminodiphenylmethane resin as in Example 5, and the laminated board and copper-clad laminate were used. A substrate was prepared, and a test was performed in the same manner as in Example 5. Example 7 The same procedure as in Example 5 was repeated except that the resin component of the resin composition was 25 parts by weight of the powdery phenolic resin and 75 parts by weight of the tetraglycidyldiaminodiphenylmethane resin as in Example 5. A substrate was prepared, and a test was performed in the same manner as in Example 5. Example 8 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5 except that the glass fiber impregnated with varnish was changed to S glass fiber having a thickness of 0.18 mm, and tested in the same manner as in Example 5. Was done. Example 9 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5 except that 3 parts by weight of the imidazole silane derivative were used in addition to 4 parts by weight of the hydrotalcite compound, and tested in the same manner as in Example 5. Was done.

Comparative Example 9 A laminated substrate and a resin composition were prepared in the same manner as in Example 5 except that the resin component of the resin composition was 90 parts by weight of the same powdery phenolic resin and 10 parts by weight of tetraglycidyldiaminodiphenylmethane resin as in Example 5. A copper-clad laminate was prepared and tested in the same manner as in Example 5. Comparative Example 10 The same procedure as in Example 5 was repeated except that the resin component of the resin composition was 10 parts by weight of the powdery phenolic resin and 90 parts by weight of the tetraglycidyldiaminodiphenylmethane resin as in Example 5, and the laminated board and the copper-clad laminate were used. A substrate was prepared, and a test was performed in the same manner as in Example 5. Comparative Example 11 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5 except that the hydrotalcite compound was not added, and a test was performed in the same manner as in Example 5. Comparative Example 12 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 6, except that the hydrotalcite compound was not added, and a test was conducted in the same manner as in Example 5. Comparative Example 13 A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 7 except that the hydrotalcite compound was not added, and a test was conducted in the same manner as in Example 5.

Comparative Example 14 The resin component of the resin composition was a novolak-type phenol resin (trade name: Shonor BRG-55 manufactured by Showa Kogyo KK).
6) A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5, except that 50 parts by weight of tetraglycidyldiaminodiphenylmethane resin was used, and the test was conducted in the same manner as in Example 5. Was done. Comparative Example 15 Except that the resin component of the resin composition was 50 parts by weight of the same powdery phenolic resin as in Example 5, and 50 parts by weight of bisphenol A / epichlorohydrin type epoxy resin (trade name: Epotote YD128 manufactured by Toto Kasei Co., Ltd.) A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5, and a test was performed in the same manner as in Example 5. Comparative Example 16 The resin component of the resin composition was 50 parts by weight of the same powdery phenolic resin as in Example 5, and a phenol novolak epoxy resin (trade name: Epototo YDPN63 manufactured by Toto Kasei Co., Ltd.)
8) A laminated substrate and a copper-clad laminated substrate were prepared in the same manner as in Example 5 except that the amount was 50 parts by weight, and a test was performed in the same manner as in Example 5. Tables 3 and 4 show the compositions and substrates of the resin compositions used in each of the examples and comparative examples, and the results of the property tests.
Shown in

[0036]

[Table 3]

[0037]

[Table 4]

Examples 5 to 8 and Comparative Example 9 shown in Tables 3 and 4
As is clear from the comparison of the results of Nos. To 16, the resin component of the specific powdery phenolic resin and the polyfunctional amine type epoxy resin having three or more glycidyl groups in the thermosetting resin laminated substrate is By using a resin composition to which a predetermined amount of a talcite compound is added, migration resistance and C resistance are achieved while achieving a low linear expansion coefficient.
The AF performance was significantly improved. Further, as is apparent from the results of Example 9, the excellent effects of the present invention were similarly obtained by using the imidazole silane derivative and the hydrotalcite compound together.

[0039]

According to the present invention, a predetermined amount of an imidazole silane derivative and / or a hydrotalcite compound is added to a resin component obtained by adding a predetermined amount of a specific polyfunctional amine type epoxy resin to a specific powdery phenolic resin. By obtaining a resin laminate using a resin composition, the crosslink density during curing can be increased, and the molecules of the polyfunctional amine-type epoxy resin to be added also have large steric hindrance and high molecular rigidity. The heat resistance and the coefficient of linear expansion can be significantly improved, and a sufficiently low coefficient of linear expansion can be realized even in combination with an E glass fiber cloth having a large linear expansion. In addition, the polyfunctional amine type epoxy resin reacts with and modifies the hydroxyl groups of the powdered phenolic resin to reduce the hydrophilic groups in the resin, and the imidazole silane derivative or hydrotalcite compound increases the growth of copper in the circuit. Due to the suppression, the water resistance and the electrical properties are also significantly improved. Also, as for the glass fiber to be used, not only S glass having high strength and low linear expansion but also sufficient properties can be obtained with less expensive E glass, so that a printed wiring board laminate is provided at lower cost. It also has the advantage of being able to do so. As described above, the resin laminated substrate of the present invention is excellent in migration resistance and CAF resistance, has heat resistance of 200 ° C. or more, and has a surface resistance of 15 p.
pm / ° C, less than 65 ppm / ° C in the thickness direction, which is a very good coefficient of linear expansion lower than that of conventional thermosetting resin laminates. It is suitable for applications where properties are required.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum of a powdery phenolic resin used in Examples of the present invention. The figure also shows a method for determining the absorption intensity at the peak of the specific wavelength.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 5/24 CFC C08J 5/24 CFC C08K 3/26 C08K 3/26 5/54 5/54 C08L 61/10 C08L 61 / 10 63/00 63/00 B H01L 23/14 H05K 1/03 610K H05K 1/03 610 H01L 23/14 R (72) Inventor Masayuki Isawa 2-6-1 Marunouchi, Chiyoda-ku, Tokyo Furukawa Electric F-term in stock (reference) 4F072 AA06 AD14 AD31 AF04 AF21 AF27 AG03 AH21 AK14 AL13 4F100 AB17 AC10A AC10H AG00B AH03A AH06A AK01A AK33A AK53A AK53K AL05A AT00B BA02 DE01A DG01B J03J03 J02J03 J02J02J02J02J02J02J02L EX076 GF00 HA09 4J036 AH07 DC40 FA06 FB07 GA28 JA08

Claims (5)

[Claims] 1. A polyfunctional amine epoxy resin (II) having three or more glycidyl groups per 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D): With respect to 100 parts by weight of the resin component containing 400 parts by weight, the following formula (1) was used. (Wherein, R ¹ and R ² each represent hydrogen or an alkyl group, and R ³ and R ⁴ each represent an alkyl group.
n represents an integer, and m represents 1, 2 or 3. A resin-laminated substrate characterized by being hot-pressed using a prepreg obtained by impregnating a substrate with a thermosetting resin composition containing 0.1 to 10 parts by weight of an imidazole silane derivative represented by the formula (1). (A) G. P. C. (Polystyrene equivalent weight average molecular weight is 1,000 or more as measured by (gel permeation chromatography); (B) free phenol content is 500 ppm or less as measured by liquid chromatography; (C) phenol Condensates of phenols and formaldehyde, (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (ii) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol (C) the trifunctional residues are phenols 2, 4 and 6
At one position and at least at another position with a methylol group and / or a methylene group, and (d) an infrared absorption spectrum according to the KBr tablet method of 1600 cm ^-1 (to benzene). Attributed absorption peak)
The absorption intensities of D ₁₆₀₀ , 990 to 1015 cm ^-1 (the absorption peak attributed to the methylol group) in the range of D _990-1015 and 890 cm ^-1 (the absorption peak of the isolated hydrogen atom in the benzene nucleus) When the strength is represented by D ₈₉₀ , the relationship of both formulas of D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7 is satisfied, and (D ) It contains spherical primary particles having a particle size of 0.1 to 100 µm and secondary aggregates thereof. 2. A polyfunctional amine type epoxy resin (II) having three or more glycidyl groups per 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D): With respect to 100 parts by weight of the resin component containing 400 parts by weight, the following formula (1) was used. (Wherein, R ¹ and R ² each represent hydrogen or an alkyl group, and R ³ and R ⁴ each represent an alkyl group.
n represents an integer, and m represents 1, 2 or 3. ) And 0.1 to 10 parts by weight of an imidazole silane derivative represented by the following formula (2): Mg _x Zn _y Al ₂ · (OH) _{2 (x + y + 2)} · (CO ₃ ) _{1 -z / 2} · ( CLO ₄ ) _z · mH ₂ O (2) (where x, y, and z each represent a number satisfying the following condition: 0 ≦ y / x <102 ≦ x + y <200 ≦ z ≦ 2, where m is 0 or any positive number.)
A resin-laminated substrate, which is heated and pressed using a prepreg obtained by impregnating a base material with a thermosetting resin composition containing 10 parts by weight. (A) G. P. C. (Polystyrene equivalent weight average molecular weight is 1,000 or more as measured by (gel permeation chromatography); (B) free phenol content is 500 ppm or less as measured by liquid chromatography; (C) phenol Condensates of phenols and formaldehyde, (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (ii) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol (C) the trifunctional residues are phenols 2, 4 and 6
At one position and at least at another position with a methylol group and / or a methylene group, and (d) an infrared absorption spectrum according to the KBr tablet method of 1600 cm ^-1 (to benzene). Attributed absorption peak)
The absorption intensities of D ₁₆₀₀ , 990 to 1015 cm ^-1 (the absorption peak attributed to the methylol group) in the range of D _990-1015 and 890 cm ^-1 (the absorption peak of the isolated hydrogen atom in the benzene nucleus) When the strength is represented by D ₈₉₀ , the relationship of both formulas of D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7 is satisfied, and (D ) It contains spherical primary particles having a particle size of 0.1 to 100 µm and secondary aggregates thereof. 3. The base material is E glass (main component: SiO ₂ 5).
2 to 56 mol% (hereinafter simply referred to as%), Al ₂ O ₃
12-16%, CaO 15-25%, MgO 0-6
_{%, B 2 O 3 8~13%} , (N 2 O + K 2 O) 0~
The resin laminated substrate according to claim 1, wherein the resin laminated substrate is made of a fiber. 4. A polyfunctional amine type epoxy resin (II) having three or more glycidyl groups per 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D): With respect to 100 parts by weight of the resin component containing 400 parts by weight, the following formula (2) Mg _x Zn _y Al ₂ · (OH) _{2 (x + y + 2)} · (CO ₃ ) _{1 -z / 2} · ( CLO ₄ ) _z · mH ₂ O (2) (where x, y, and z each represent a number satisfying the following condition: 0 ≦ y / x <102 ≦ x + y <200 ≦ z ≦ 2, where m is 0 or any positive number.)
A resin-laminated substrate, which is heated and pressed using a prepreg obtained by impregnating a base material with a thermosetting resin composition containing 10 parts by weight. (A) G. P. C. (Polystyrene equivalent weight average molecular weight is 1,000 or more as measured by (gel permeation chromatography); (B) free phenol content is 500 ppm or less as measured by liquid chromatography; (C) phenol Condensates of phenols and formaldehyde, (a) is substantially composed of carbon, hydrogen and oxygen atoms, and (ii) a main bond of a methylene group, a methylol group, and a trifunctional residue of a phenol (C) the trifunctional residues are phenols 2, 4 and 6
At one position and at least at another position with a methylol group and / or a methylene group, and (d) an infrared absorption spectrum according to the KBr tablet method of 1600 cm ^-1 (to benzene). Attributed absorption peak)
The absorption intensities of D ₁₆₀₀ , 990 to 1015 cm ^-1 (the absorption peak attributed to the methylol group) in the range of D _990-1015 and 890 cm ^-1 (the absorption peak of the isolated hydrogen atom in the benzene nucleus) the strength when expressed _{89 0} in, D, satisfies the both equations of the relationship _{D 990-1015 / D 1600 = 0.2~9.0 D} 890 / D 1600 = 0.05~0.7, and ( D) It contains spherical primary particles having a particle size of 0.1 to 100 μm and secondary aggregates thereof. 5. The polyfunctional amine type epoxy resin (I)
5. The resin laminated substrate according to claim 1, wherein I) is an aromatic glycidylamine type polyfunctional epoxy resin obtained from a reaction between an aromatic amine and epichlorohydrin.