JP2000006315A - Thermosetting resin laminated sheet for printed-wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve matching of coefficients of linear expansion in both surface direction and thickness direction by manufacturing a laminated sheet using a prepreg, wherein a resin composition composed by blending a specified amount of a specified multi-functional epoxy resin with a specified thermosetting powdered phenolic resin is impregnated with a glass fiber fabric. SOLUTION: A powdered phenolic resin is composed of a condensate of a phenol and a formaldehyde by making an average molecular weight of polystyrene 1000 or higher, and an amount of a free phenol contained 500 ppm or lower. An infrared absorption spectrum of the resin exhibits a maximum absorption intensity of 0.2-9.0 in a range of 1600 cm-1 and an absorption intensity of 0.05-0.7 in a range of 890 cm-1, and the resin contains secondary agglomerates of spherical primary particles having a particle diameter of 0.1-100 μm. A resin composition, wherein 50-450 wt.pts. multi-functional epoxy resin having three or more glycidel groups is blended with the 100 wt.pts. of the resin, is impregnated to a glass fiber fabric for forming a prepreg, and a laminated sheet is manufactured therefrom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin laminate used as a material for a printed wiring board or the like, which is a component of an electronic device or the like, and a method for producing the same. The present invention relates to a thermosetting resin laminate excellent 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 when a package form such as a multichip module is required to have a heat resistance of 200 ° C or more as in a normal semiconductor package. Printed wiring boards have been used. However, ceramic printed wiring boards are more brittle and difficult to handle than ordinary resin printed wiring boards, it is difficult to manufacture multilayer boards with more than two layers, it is difficult to improve wiring density, and manufacturing costs are high. There was a problem. For this reason, recently, the use of a resin printed wiring board in which a high heat-resistant resin such as a bismaleimide triazine resin (BT resin), a polyimide resin, or a high heat-resistant epoxy resin is combined with a fiber cloth such as glass or aramid is increasing. ing.

On the other hand, these printed wiring boards made of high heat-resistant resin are also required to match the coefficient of linear expansion in the plane direction with the semiconductor chip (10 ppm / ° C. or less), and to ensure the reliability of through holes in the thickness direction of the substrate. Of the coefficient of thermal expansion of the copper plating in the through-hole with the coefficient of linear expansion (about 30 ppm / ° C.), heat resistance enough to withstand several times of soldering (glass transition temperature Tg: 200 ° C. or higher, 260 ° C. Solder heat resistance: At present, there is no one that is sufficiently satisfactory in terms of cost and the like. For example, in the case of a structure in which a high heat resistant epoxy resin is impregnated into a glass fiber cloth, the linear expansion coefficient in the plane direction is 15 to 20 ppm / ° C.
It is as large as 0 ppm / ° C. and has a heat resistance of about 140 ° C., which is insufficient for applications such as a multi-chip module. In the case of a substrate using high strength, low linear expansion S glass or T glass for the glass fiber, the linear expansion coefficient in the plane direction is 1
Although relatively small at 0 ppm / ° C., it is 6 in the thickness direction.
The heat resistance is as large as 0 ppm or more and the Tg is 170 ° C. to 18 ° C.
It was insufficient at 0 ° C. On the other hand, a substrate in which a glass fiber cloth is impregnated with a high heat-resistant thermosetting resin such as a polyimide resin or a BT resin has a good Tg of 200 ° C. or higher in terms of heat resistance, but has a linear expansion coefficient of epoxy resin made of glass fiber. It was about the same as the cloth impregnated, and was much more expensive than the glass epoxy substrate.

Japanese Patent Application Laid-Open No. Hei 6 (1994) discloses an example of using a resin composition of a phenolic resin and an epoxy resin for a laminate.
JP-A-97596, JP-T-7-509022,
JP-B-62-35417, JP-A-58-1520
No. 45, JP-A-1-74211, JP-A-2-
No. 129233, JP-A-2-129234, and the like. However, none of the techniques described in these publications satisfy the characteristics required for a printed wiring board, such as the linear expansion coefficient and heat resistance of a laminate. For example, first, Japanese Patent Application Laid-Open No. Hei 6-97596 discloses a printed wiring board using a composition of a novolak type phenol resin and various epoxy resins, but the printed wiring board shown there has a low Tg, The evaluation of solder heat resistance is 260 ° C. × 20 seconds, which is insufficient heat resistance.
Next, Japanese Patent Application Laid-Open No. 7-509022 discloses a phenol-curable epoxy resin molding compound, and a composition containing a glycidylamine type epoxy resin is also exemplified. It is a modified resin of a phenol resin or a novolak resin, and a laminate obtained from this resin composition has insufficient linear expansion coefficient and heat resistance. Further, there is no disclosure of an example in which a glycidylamine type epoxy resin is used alone.

[0005] JP-A-1-74211 and JP-A-2-129234 disclose a prepreg using a composition comprising a powdery phenolic resin or a usual resol resin or a novolak resin, various epoxy resins and a filler. Although disclosed, they do not satisfy electrical characteristics, heat resistance, linear expansion coefficient, and the like, which are important characteristics as a printed wiring board for electronic components. Further, JP-A-58-113243, JP-A-58-1
JP-A-52045 discloses a resin composition comprising a powdery phenolic resin, another thermosetting resin, and a filling material. Examples of the thermosetting resin include various epoxy resins and a filling material such as glass fiber. However, the heat resistance, the coefficient of linear expansion and the like were not satisfied. Further, JP-A-2-129233 discloses a thermosetting resin solution using a powdered phenolic resin. However, it is only exemplified in detail when the phenolic resin alone is used as a resin solution, and the disclosed characteristics are limited to only mechanical characteristics, and the disclosure of technology relating to electrical characteristics and the like important as a printed wiring board is disclosed. No description is given, and there is no description of a specific compounding ratio of a composition with another resin, for example, a composition with an epoxy resin or the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and has good linear expansion coefficient matching in both the plane direction and the thickness direction, has excellent heat resistance, and has a conventional glass epoxy. An object of the present invention is to provide a low-cost thermosetting resin laminate for a printed wiring board as well as a substrate.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a specific amount of a specific polyfunctional epoxy resin has been added to a specific thermosetting powdery phenolic resin. The present inventors have found that the above object can be achieved by manufacturing a laminate using a prepreg in which a glass fiber cloth is impregnated with a blended resin composition, and have completed the present invention.

That is, the present invention provides the following inventions (1) and (2). (1) 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D), and a polyfunctional epoxy resin (II) having three or more glycidyl groups:
A thermosetting resin laminate for a printed wiring board, wherein a plurality of prepregs obtained by impregnating a resin composition containing 450 parts by weight into a glass fiber cloth are laminated and heated and pressed. (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). the absorption intensity of the absorption peak) when expressed in D _890,, a _{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. (2) The printed wiring board according to (1), wherein the polyfunctional epoxy resin (II) is an aromatic glycidylamine type polyfunctional epoxy resin obtained by a reaction between an aromatic amine and epichlorohydrin. Thermosetting resin laminate.

[0009]

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 specified 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 (C) and (C) three main binding units of a methylene group, a methylol group, and a trifunctional residue of a phenol. D) to satisfy the relationship specified in (d). 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, the absorption intensity in the infrared absorption spectrum defined in the above (C) and (d) is obtained 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.

The powdery phenol 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. In addition, with respect to the powdery phenol resin used in the present invention, G.P. P. C. Is less than 1,000 in terms of polystyrene, and the absorption intensity in the infrared absorption spectrum is D _990-1015.
/ D ₁₆₀₀ and / or D ₈₉₀ / D ₁₆₀₀ have a value lower than the lower limit of the 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 a novolak resin or a resol resin, and has an appropriate reactive methylol group. Is contained. The 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.

(II) Polyfunctional epoxy resin In the present invention, a polyfunctional epoxy resin having three or more glycidyl groups is used. The polyfunctional epoxy resin is preferably an aromatic glycidylamine type polyfunctional epoxy resin obtained by reacting an aromatic amine such as diaminodiphenylmethane, metaxylylenediamine and 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 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.

In the present invention, the polyfunctional epoxy resin (II) is 50 to 450 parts by weight, preferably 60 to 420 parts by weight, based on 100 parts by weight of the powdery phenolic resin (I).
Parts by weight, more preferably 67 to 400 parts by weight, to obtain a resin composition. If the amount of the polyfunctional epoxy resin is too small, the water absorption of the laminate will be high (moisture resistance will be low), and the migration resistance will be low. Becomes larger,
This is not preferable because the reliability at the time of mounting the chip deteriorates.
Further, for the purpose of improving the flame resistance of the laminate in the present invention, a halogen compound such as a brominated bisphenol A type epoxy resin, a phosphorus compound such as cresyl diphenyl phosphate, zinc borate, an inorganic flame retardant such as aluminum hydroxide, Other flame retardants may be added to the resin composition.

Hereinafter, the production of the thermosetting resin laminate for a printed wiring board of the present invention from the above 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 resin composition containing the powdered phenolic resin (I) and the polyfunctional epoxy resin (II) is dissolved in an appropriate solvent such as methyl ethyl ketone to obtain a resin solution. Alternatively, after dissolving the resins (I) and (II), their solutions may be simply mixed or a solvent may be added or mixed. Next, the obtained resin solution was mixed with S glass cloth or E glass.
A prepreg is obtained by impregnating a glass fiber cloth such as a glass cloth and removing the solvent by heating and drying. The glass fiber cloth may be previously subjected to a surface treatment by a silane coupling treatment or the like. Next, two or more, preferably two to four, prepregs are stacked, heated and pressed, and after-cured to obtain the printed wiring board laminate of the present invention. The thickness of the thermosetting resin laminate for a printed wiring board of the present invention is not particularly limited, but is usually 0.05 to 1.5 mm.

[0017]

The present invention will be described in more detail with reference to the following examples. The method of the characteristic test is described below. (1) Coefficient of linear expansion Measured in accordance with JIS C6481. The obtained laminated plate was placed in a plane direction: 1.0 cm × 0.5 cm, a thickness direction: 0.1 cm.
A sample cut into 5 cm × 0.5 cm is used as a sample, a load of 2 g is applied to the sample, and the temperature is raised at a rate of 2 ° C./min.
The coefficient of linear expansion measured in the temperature range is indicated by an average value in each of the surface direction and the thickness direction of the sample. A coefficient of linear expansion of 10 or less in the plane direction and a value of 60 or less in the thickness direction are regarded as acceptable, and those exceeding these values are regarded as reject. (2) Glass transition temperature According to JIS C4681, T
It was measured by the MA method. From the point of heat resistance, 200 ° C or more is accepted, and less than 200 ° C is rejected. (3) 260 ° C. Solder Heat Resistance The obtained laminate was tested according to JIS C6481. It was immersed in a 260 ° C. solder bath and the time (seconds) until blistering occurred on the surface copper foil was shown. From the viewpoint of heat resistance, 180 seconds or more is passed, and less than 180 seconds is rejected. (4) Water absorption The test was carried out according to JIS C6481. The smaller the number,
It means that water absorption is good. (5) Volume resistivity It was tested according to JIS C6481. (6) Dielectric constant, dielectric loss tangent It was tested according to JIS C6481. (7) Migration Resistance (Electrical Characteristics) A comb-shaped counter electrode (wiring width 0.1 mm, gap between wirings 0.1 mm) is formed on the surface of a copper-clad laminate having a copper foil layer provided on both sides by etching, and 85 DC 5% at 85% RH
A voltage of 0 V was applied. The results are shown as the time (hour) during which the resistance value of 10 ⁸ Ω or more was maintained. As a laminate for a printed wiring board, a laminate having a result of 1000 hours or more is regarded as pass, and a laminate having a result of less than 1000 hours is rejected.

(Example 1) Thermosetting powdery phenolic resin [trade name: Bellpearl S890 manufactured by Kanebo Co., Ltd.] 1
00 parts by weight and tetraglycidyldiaminodiphenylmethane resin [trade name: Epototo YH manufactured by Toto Kasei Co., Ltd.]
-434, epoxy equivalent of 110 to 140 g / eq] 10
0 parts by weight dissolved in methyl ethyl ketone and 50% by weight
This was a resin solution. This resin solution was impregnated into a glass fiber cloth (S glass cloth, 0.18 mm thick) which had been previously surface-treated with a silane coupling agent, and dried by heating to obtain a prepreg. Three prepregs were laminated, and the temperature was 1
The laminate was manufactured by hot pressing at 80 ° C. After this laminate was after-cured at 240 ° C., it was allowed to cool to 25 ° C. to obtain a laminate for a printed wiring board. The characteristics of the obtained laminate for a printed wiring board were tested. In the test of the electrical characteristics, a copper-clad laminate in which a 9-μm-thick copper foil was pressed simultaneously on both front and back surfaces during lamination pressing was used. Table 1 shows the results. It can be seen that good results were obtained for all the characteristics.

(Example 2) Thermosetting powdery phenolic resin [trade name: Bellpearl S890 manufactured by Kanebo Co., Ltd.] 1
00 parts by weight and 150 parts by weight of a tetraglycidyldiaminodiphenylmethane resin were dissolved in methyl ethyl ketone to prepare a 50% by weight resin solution. Hereinafter, a laminate was prepared under the same conditions as in Example 1 except that E glass cloth (0.18 mm thick) was used as the glass fiber cloth, and various characteristics were tested. The results are shown in Table 1. From Table 1, it can be seen that the same results as those of Example 1 using S glass were obtained in both linear expansion coefficient and heat resistance. (Examples 3 and 4) Laminates were prepared and subjected to similar tests in the same manner as in Example 1 except that the compositions and the laminates shown in Table 1 were changed. The results are shown in Table 1. In each of the examples, the linear expansion coefficient, the heat resistance, and the electrical characteristics show good results.

[0020]

[Table 1]

Comparative Example 1 A thermosetting powdery phenolic resin (trade name: Bellpearl S890) was laminated in the same manner as in Example 1 except that 200 parts by weight was dissolved in methyl ethyl ketone to prepare a 50% by weight resin solution. A board was prepared and a similar test was performed. Table 2 shows the results. The properties were lower than those of the examples, and the results were particularly poor in water absorption and migration resistance. (Comparative Example 2) 100 parts by weight of a thermosetting powdery phenolic resin [trade name: Bellpearl S890] and 40 parts by weight of a tetraglycidyldiaminodiphenylmethane resin were dissolved in methyl ethyl ketone to form a 50% by weight resin solution, and then implemented. A laminate was prepared in the same manner as in Example 1, and a similar test was performed. Table 2 shows the results. It can be seen that heat resistance, coefficient of linear expansion, water absorption, and migration resistance are inferior to each of the examples.

Comparative Example 3 100 parts by weight of thermosetting powdery phenolic resin [trade name: Bellpearl S890] and tetraglycidyldiaminodiphenylmethane resin 5
After dissolving 00 parts by weight in methyl ethyl ketone to obtain a 50% by weight resin solution, a laminate was prepared in the same manner as in Example 2, and the same test was performed. Table 2 shows the results. As a result, the coefficient of linear expansion was significantly inferior to those of the examples. (Comparative Example 4) High heat-resistant glass epoxy laminate [Equivalent to American Electrical Industry Standard (NEMA) FR-5, thickness 0.6 m
m], various characteristics were evaluated in the same manner as in Example 1. The results are shown in Table 2. The linear expansion coefficient in the thickness direction and heat resistance were poor.

Comparative Example 5 Thermosetting powdery phenolic resin [trade name: Bellpearl S890 manufactured by Kanebo Co., Ltd.] 1
100 parts by weight and 100 parts by weight of a phenol novolak type epoxy resin [trade name: BREN-S manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 280 g / eq, bromine content: 35%] are dissolved in methyl ethyl ketone to obtain 50% by weight. After preparing the resin solution, a laminate was prepared in the same manner as in Example 2, and the same test was performed. The results are shown in Table 2. Although the water absorption and the initial electrical characteristics were good, the solder heat resistance at 260 ° C. and the migration resistance were remarkably inferior to those of the examples. (Comparative Example 6) Novolak resin as a phenolic resin [trade name: Shownol BRG-5 manufactured by Showa Polymer Co., Ltd.]
56] 100 parts by weight and tetraglycidyl diaminodiphenylmethane resin [trade name: Epotote YH-434 manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 110 to 140 g / e]
q] 120 parts by weight in methyl ethyl ketone
After the resin solution was 0% by weight, a laminate was prepared in the same manner as in Example 1 and the same test was performed. The results are shown in Table 2. The linear expansion coefficient and the heat resistance were extremely poor.

Comparative Example 7 Thermosetting powdery phenolic resin [trade name: Bellpearl S890 manufactured by Kanebo Co., Ltd.] 1
100 parts by weight and a bisphenol A type epoxy resin [trade name: Epototo YDB-400 manufactured by Toto Kasei Co., Ltd., epoxy equivalent 400 g / eq, bromine content 48%] 100
The resin was dissolved in methyl ethyl ketone to obtain a 50% by weight resin solution. Then, a laminate was prepared in the same manner as in Example 2 and the same test was performed. The results are shown in Table 2.
Water absorption, initial electrical properties, etc. were good,
As in Comparative Example 5, the solder heat resistance at 260 ° C. and the migration resistance were extremely poor.

[0025]

[Table 2]

Table 3 shows 99 of the phenolic resins used in Examples and Comparative Examples as measured by infrared absorption spectroscopy.
160 with an absorption intensity of 0-1015 cm ^-1 and 890 cm ^-1
The results for the ratio to the absorption intensity of 0 cm ^-1 (IR absorption intensity ratio), the weight average molecular weight, and the particle size of the primary particles are shown.

[0027]

[Table 3]

Comparative Example 8 Reference Example 1 described in JP-B-62-35417, Run No. A powdery phenol resin was synthesized using the raw materials and the production method of No. 6, and the IR absorption intensity ratio was measured. A varnish having the same resin ratio as in Example 1 was prepared, a laminate was prepared, and the gel time of the varnish at 150 ° C. and the glass transition temperature of the laminate by the TMA method were measured. Table 4 shows the results. This shows that although the heat resistance is excellent, the gel time at 150 ° C. is short, the prepreg is excessively hardened, and the appearance of the laminate is poor. (Reference Example) Reference Example 1, Run No. 1 described in JP-B-62-35417. A powdery phenol resin was synthesized using the raw materials and manufacturing method of No. 10, and the same evaluation as in Comparative Example 8 was performed.
As shown in Table 4, the gel time at 150 ° C. was longer than that of Example 1 and the storage stability of the varnish was good and the appearance of the laminate was good, but the heat resistance of the laminate was slightly inferior. Was.

[0029]

[Table 4]

[0030]

According to the present invention, a laminate for a printed wiring board is obtained by using a resin composition in which a predetermined amount of a specific polyfunctional epoxy resin is added to a specific powdery phenolic resin. In addition to increasing the crosslink density at the time, the added epoxy resin molecule itself has a large steric hindrance, and the rigidity of the molecule is high, so the heat resistance and linear expansion coefficient can be greatly improved, and the linear expansion is usually large. Even in combination with the E glass fiber cloth, a sufficiently low linear expansion coefficient can be realized. Further, the epoxy resin reacts with the hydroxyl group of the powdery phenolic resin to reduce the number of hydrophilic groups in the resin, thereby contributing to the improvement of water resistance and electric characteristics. 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 thermosetting resin laminate of the present invention has a heat resistance of 200 ° C. or more, and has a heat resistance of 1
0 ppm / ° C or less, and 60 ppm / ° C or less in the thickness direction, which is a very good linear expansion coefficient lower than that of a conventional thermosetting resin laminate, so that it has high heat resistance and high dimensional stability especially for multichip modules and the like. 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) H05K 1/03 610 H05K 1/03 610K 610L

Claims (2)

[Claims] 1. A polyfunctional epoxy resin (I) having three or more glycidyl groups per 100 parts by weight of a powdery phenolic resin (I) having the following characteristics (A) to (D):
I) A thermosetting resin laminate for a printed wiring board, wherein a plurality of prepregs obtained by impregnating a resin composition containing 50 to 450 parts by weight into a glass fiber cloth are laminated and heated and pressed. (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 , D _990-1015 / D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.05 to 0.7, and (D) the particle size is 0. It contains spherical primary particles of 1 to 100 μm and secondary aggregates thereof. 2. The polyfunctional epoxy resin (II) comprises:
The thermosetting resin laminate for a printed wiring board according to claim 1, which is an aromatic glycidylamine-type polyfunctional epoxy resin obtained by a reaction between an aromatic amine and epichlorohydrin.