JPH11279373A - Resin composition for printed circuit board, and laminate for printed circuit board, laminate for multilayer printed circuit board, and semiconductor device of ball grid array type prepared by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin compsn. for printed circuit boards which gives a cured item having resistances to heat and moisture, adhesive power, and resistance to soldering heat. SOLUTION: This compsn. is prepd. by compounding (a) a cyclopentadiene epoxy resin of the formula (wherein 1 is an integer of, on average, 0-3), (b) tetrabromobisphenol A, (c) a phenol resin excluding tetrabromobisphenol A, and (d) a cure catalyst for accelerating the reaction of epoxy group with phenolic hydroxyl group, the amt. of tetrabromobisphenol A compounded being 30-38 wt.% of the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a printed circuit, a printed circuit board using the same,
The present invention relates to a multilayer board for a multilayer printed circuit and a ball grid array type semiconductor device.

[0002]

2. Description of the Related Art In recent years, there has been remarkable innovation in packaging technology corresponding to miniaturization and high density of electronic equipment, and in response to this, new technologies are required for printed circuit laminates and semiconductor devices. . Among them, a ball grid array type semiconductor device in which a semiconductor element is mounted on a printed circuit laminate and solder balls are formed in a grid on the back surface on which the semiconductor is mounted, that is, a BGA (ball grid array) package is large. Attracting attention. The BGA package is a new surface-mount type multi-terminal semiconductor package that uses a printed circuit laminate. It has a smaller outer shape than conventional semiconductor packages in which semiconductor elements are mounted on a lead frame and resin-sealed, making it easier to increase the number of terminals In addition, since it can be easily soldered to a printed circuit laminate, it has been increasingly used in electronic devices.

The above-mentioned semiconductor package is a new application of a printed circuit laminate because it has a structure in which a lead frame used so far is replaced with a printed circuit laminate. Due to the trend toward multi-terminals, a large market is expected, and development is being actively conducted. However, for printed circuit laminates, BG
Since there is no specially developed package for semiconductor packages such as A package, it is currently used for conventional glass epoxy printed circuit laminates called FR-4 and printed circuits using bismaleimide-triazine (BT) resin. Laminates are used.

However, for example, a printed circuit laminate for a semiconductor package such as a BGA package has characteristics (1) in addition to the characteristics required for a conventional printed circuit laminate.
It is necessary to have heat resistance, (2) moisture resistance, (3) adhesive strength, and (4) solder heat resistance.

[0005] Heat resistance is required to cope with semiconductor package assembly processes at high temperatures such as die bonding, wire bonding, and resin sealing. Generally, the heat resistance is determined by the glass transition temperature of the cured product of the resin composition for a printed circuit as an index. In order to cope with a semiconductor package assembling process, a glass transition temperature of 150 ° C. or higher, preferably 160 ° C. or higher is required.

Since the semiconductor package is used under high-temperature and high-humidity conditions, the moisture resistance of the materials used for the semiconductor package is also required to ensure the reliability. For this reason, the reliability of a semiconductor package containing a semiconductor is evaluated under severe high-temperature and high-humidity conditions (such as 121 ° C./100%/2 atm.) Called a pressure cooker test. It is necessary to ensure the moisture resistance reliability of the laminated board under these conditions.

Further, a semiconductor device is mounted on a printed circuit laminate or a multilayer printed circuit laminate, and solder balls are formed in a grid on the back surface of the semiconductor side. There is a package crack generated in the semiconductor package at the time of solder reflow. That is, the semiconductor package absorbs moisture in the air and the moisture accumulates in the semiconductor package, and the absorbed semiconductor package is heated to a high temperature during solder reflow for soldering to the printed circuit board, and accumulates in the semiconductor package. Cracks are generated in the semiconductor package because the water vaporizes rapidly and turns into water vapor. In order to prevent the occurrence of cracks in the semiconductor package, it is important to reduce the amount of water absorption and to improve the adhesive strength, in addition to the solder heat resistance of the printed circuit laminate used in the semiconductor package after moisture absorption.

However, since the glass transition temperature of a cured resin composition for a printed circuit used in FR-4, which is widely and generally used as a printed circuit laminate, is about 130 ° C., heat resistance is insufficient. In addition, the semiconductor package assembly process cannot be performed at a high temperature, and sufficient performance and reliability cannot be obtained as a semiconductor package. The resin composition for a printed circuit used in FR-4 uses dicyandiamide as a curing agent, so that the cured resin has a high polarity and a large amount of water absorption, and further has a high temperature of 121 ° C./100%/2 atm. Under high humidity conditions, the resin is hydrolyzed and the resin itself is decomposed.

Further, BT resin, which is widely used as a printed circuit laminate for a semiconductor package at present, has high heat resistance but low moisture resistance, a large amount of water absorption, and under high temperature and high humidity conditions, a bismaleimide resin. Since the imide bond is hydrolyzed and the resin itself is decomposed, and the adhesive strength is low, there is a problem that the package crack resistance is low.

Also, when an acid anhydride curing agent is used as a curing agent for the epoxy resin, the cured resin is three-dimensionally cross-linked by an ester bond. Since the resin is decomposed, the resin itself is decomposed.

As described above, a cured product of a resin composition for a printed circuit comprising an epoxy resin and dicyandiamide, a cured product of a resin composition for a printed circuit comprising an epoxy resin and an acid anhydride, and a material for a printed circuit having high heat resistance. BT
Since the cured resin easily undergoes hydrolysis under high-temperature and high-humidity conditions and the resin itself decomposes, the printed circuit laminate obtained using these resin compositions is used for semiconductor packages. However, sufficient performance and reliability cannot be obtained as a semiconductor package, which is a problem.

That is, when a conventional printed circuit laminate using FR-4 is used for a semiconductor package, it cannot cope with a semiconductor high-temperature assembling process, and sufficient performance and reliability can be obtained as a semiconductor package. There were no problems. Furthermore, printed circuit laminates using FR-4 and B
When a printed circuit laminate using a T resin is used for a semiconductor package, there is a problem that moisture resistance is not sufficient and sufficient performance and reliability as a semiconductor package cannot be obtained under high temperature and high humidity conditions.

In addition, the wiring of a printed circuit laminate for a semiconductor package such as a BGA package is required to have a finer and higher density. 2. Description of the Related Art The development of a multilayer printed circuit board by a build-up method of manufacturing by stacking and connecting layers sequentially has been active. A multilayer printed circuit laminate manufactured by a build-up method has a high degree of freedom in wiring and can further reduce the thickness of an insulating layer and a conductive layer.
However, a multilayer printed circuit laminate manufactured by a build-up method using a conventional printed circuit laminate using FR-4 or a BT resin printed circuit laminate as a support substrate does not have sufficient moisture resistance of the support substrate. However, when used in a semiconductor package, the crack resistance and moisture resistance of the semiconductor package are low, which poses a problem.

On the other hand, a laminate for a printed circuit using a resin composition for a printed circuit obtained by curing a phenolic resin of an epoxy resin which does not cause hydrolysis under high temperature and high humidity conditions has been studied. For this reason, an amine curing agent such as dicyandiamide is often used in combination, and when an amine curing agent such as dicyandiamide is used in combination, heat resistance and adhesive strength are improved, but moisture resistance is greatly reduced, water absorption is large, and high temperature Under wet conditions, hydrolysis occurs and the resin itself decomposes. When not using an amine curing agent,
Although it does not cause hydrolysis under high temperature and high humidity conditions and has high moisture resistance,
There has been a problem that the adhesive strength and the solder heat resistance are lower than those using an epoxy resin composition using dicyandiamide as a curing agent as an amine curing agent. In particular, when the heat resistance is improved, the adhesive strength and the solder heat resistance are large and decrease in inverse proportion to the heat resistance.

[0015] Japanese Patent Application Laid-Open Nos. Hei 7-90047 and Hei 8-111571 disclose cyclopentadiene-type epoxy resins, tetrabromobisphenol A, and the like. Cyclopentadiene-type phenolic resins have been disclosed, and attempt to achieve a low coefficient of thermal expansion. JP-A-7-126346 discloses a laminate for a printed circuit board using a resin composition comprising a cyclopentadiene-type epoxy resin, tetrabromobisphenol A and a phenol resin having a menthane skeleton. Trying to achieve.

[0016]

However, the above publication examines the optimum compounding amount which gives the above-mentioned optimal performance (heat resistance, moisture resistance, adhesiveness, solder heat resistance) as a printed circuit laminate. Not. In addition, when a printed circuit laminate is formed into a multilayer printed circuit laminate by a build-up method, no consideration has been given to using it for a support substrate or a semiconductor device. Furthermore, conventional printed circuit laminates using a phenolic resin having a menthol skeleton,
There is a problem that the reactivity between the phenol resin having a menthane skeleton and the epoxy resin is low, and in particular, the solder heat resistance is greatly reduced. In other words, even if the phenolic resin-cured epoxy resin disclosed in the above publication is used, it does not cause hydrolysis under high-temperature and high-humidity conditions and has high moisture resistance, but particularly when heat resistance is improved, adhesive strength and solder heat resistance are increased. The problem of significant reduction is not solved.

That is, as described above, a printed circuit laminate for a semiconductor package such as a BGA package is provided with:
To prevent cracks during reflow and ensure semiconductor reliability, in addition to the characteristics required for conventional printed circuit laminates,
It is necessary to have (1) heat resistance, (2) moisture resistance, (3) adhesive strength, and (4) soldering heat resistance. Conventional printed circuit laminates have these characteristics. There was no.

The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to obtain a resin composition for a printed circuit having a cured product having heat resistance, moisture resistance, adhesive strength, and soldering heat resistance. . It is another object of the present invention to provide a printed circuit board or a multilayer printed circuit board which is excellent in high heat resistance, low water absorption, high adhesion and solder heat resistance, and is preferably used for semiconductor packages such as BGA packages. Another object is to obtain a ball grid array type semiconductor device having high crack resistance and high reliability.

[0019]

The first resin composition for a printed circuit according to the present invention has the following general formula (1):

[0020]

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Wherein, in the formula, 1 is an integer of 0 to 3 on average, cyclopentadiene type epoxy resin (a), tetrabromobisphenol A (b), and phenol resins other than tetrabromobisphenol A (b) ( c) and a curing catalyst (d) for accelerating the reaction between the epoxy group and the phenolic hydroxyl group. The compounding amount of the tetrabromobisphenol A (b) is 30 to 38% by weight of the whole composition.

The second resin composition for a printed circuit according to the present invention is the same as the first resin composition for a printed circuit, except that the cyclopentadiene-type epoxy resin (a), the tetrabromobisphenol A (b) and the phenol resin ( c) is blended such that the ratio of phenolic hydroxyl group to epoxy group (phenolic hydroxyl group / epoxy group) is 0.98 to 1.02.

The third resin composition for a printed circuit according to the present invention is the resin composition for a printed circuit according to the first or second embodiment, wherein the phenolic resin (c) is represented by the following general formula (2):

[0024]

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A bisphenol A novolak resin represented by the following formula (where m is an integer of 0 to 8 on average):

[0026]

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(Where n is an integer of 0 to 5 on average) a triphenylmethane type phenol resin represented by the following general formula (4):

[0028]

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(Wherein p is an integer of 0 to 8 on average).

The fourth resin composition for a printed circuit according to the present invention is the same as the resin composition for a printed circuit according to any one of the first to third above, except that the chemical formula (5)

[0031]

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The polyfunctional epoxy resin (e) represented by the formula (1) is mixed with 10 to 23% by weight of the whole composition.

The first printed circuit laminate according to the present invention is obtained by providing a conductive layer on at least one surface of an insulating material impregnated with any of the first to fourth printed circuit resin compositions. .

A second printed circuit laminate according to the present invention is the first printed circuit laminate described above, wherein the conductive layer is patterned.

The first multilayer printed circuit laminate according to the present invention is obtained by alternately laminating insulating layers and conductive layers on the second printed circuit laminate in this order by a build-up method.

In the first ball grid array type semiconductor device according to the present invention, a semiconductor element is provided on one surface of the second printed circuit laminate or the first multilayer printed circuit laminate, and the other is provided. A solder ball is formed on the surface.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION A resin composition for a printed circuit according to a first embodiment of the present invention comprises a cyclopentadiene type epoxy resin (a) represented by the above general formula (1) and tetrabromobisphenol A (b) ), A phenolic resin (c) other than tetrabromobisphenol A (b), and a curing catalyst (d). Particularly, the blending amount of the above tetrabromobisphenol A (b) is 30 to 30% of the total composition.
38% by weight. The curing catalyst (d) promotes the reaction between the epoxy group of the epoxy resin (a) and the phenolic hydroxyl group of the tetrabromobisphenol A (b) and the phenol resin (c).

The amount of tetrabromobisphenol A (b) greatly affects the adhesive strength, solder heat resistance and heat resistance required for a printed circuit laminate for a semiconductor package. FIGS. 4, 5 and 6 show the glass transition temperature and the interlayer adhesion of a cured product of the printed circuit resin composition according to the amount of tetrabromobisphenol A (TBBA) in the printed circuit resin compositions shown in the following examples. FIG. 4 is a characteristic diagram showing a change in strength and a solder heat resistance test pass rate. The figure shows the printed circuit resin compositions using various phenolic resins (c) by black squares, black circles, and black triangles, respectively. As is clear from the figure, the adhesive strength and the solder heat resistance are improved to about 34% by weight together with the amount of tetrabromobisphenol A, and then saturated and show almost constant values. In addition, the glass transition temperature, which is an index of heat resistance, decreases with the amount of tetrabromobisphenol A, because tetrabromobisphenol A has only two phenolic hydroxyl groups in the molecule. From the correlation between the adhesive strength, the solder heat resistance and the glass transition temperature and the amount of tetrabromobisphenol A, the amount of tetrabromobisphenol A must be sufficient to provide sufficient characteristics as a printed circuit laminate for a semiconductor package. From 30 to 3 of the entire resin composition
It can be seen that it is necessary to be 8% by weight. 30
If it is less than the weight percentage, it is a measure of the adhesive strength required for a printed circuit laminate for a semiconductor package, which is 1.0.
Kgf / cm or more of the interlayer adhesive strength is not obtained, and the soldering heat resistance is not preferable because the pass rate is half or more at 320 ° C. When the amount of tetrabromobisphenol A exceeds 38% by weight of the whole resin composition, the crosslink density of the cured product decreases because tetrabromobisphenol A has only two phenolic hydroxyl groups in the molecule, and the glass transition temperature is lowered. Decreases to 160 ° C. or lower.

The above-mentioned tetrabromobisphenol A
As (b), commercially available products can be widely used. Tetrabromobisphenol A is essential for improving the properties of printed circuit laminates. Compared with the properties of printed circuit laminates cured only with other phenolic resin (c), tetrabromobisphenol A (b) and other Curing agent system mixed with phenolic resin (c)
Solder heat resistance is greatly improved.

In the resin composition for a printed circuit, the cyclopentadiene type epoxy resin (a), the tetrabromobisphenol A (b) and the phenol resin (c) have a phenolic hydroxyl group to epoxy group ratio of 0.98 to 1.98. 02. The ratio of the phenolic hydroxyl group to the epoxy group greatly affects the heat resistance, adhesive strength, and solder heat resistance required for a printed circuit laminate for a semiconductor package. FIGS. 1, 2 and 3 each show a glass of a cured product of a printed circuit resin composition according to the ratio of phenolic hydroxyl groups to epoxy groups (phenolic hydroxyl group / epoxy group) in the printed circuit resin compositions shown in the following examples. FIG. 4 is a characteristic diagram showing changes in a transition temperature, an interlayer adhesive strength, and a pass rate of a solder heat resistance test at 320 ° C. The figure shows the printed circuit resin compositions using various phenolic resins (c) by black squares, black circles, and black triangles, respectively. From the figure, the heat resistance, adhesive strength and solder heat resistance show the highest characteristics when the ratio of phenolic hydroxyl group to epoxy group is around 1.00. In order to provide sufficient characteristics as a printed circuit laminate for a semiconductor package, it is desirable that the ratio of the phenolic hydroxyl group to the epoxy group be 0.98 to 1.02. The cyclopentadiene-type epoxy resin has a rigid structure in which a dicyclopentadienelen group, which is an aliphatic cyclic skeleton, is polyadded to phenol without passing through a methylene group. Therefore, it is considered that the single reaction of the epoxy resin is unlikely to occur, and the reaction between the epoxy group and the phenolic hydroxyl group of the curing agent is mainly performed.

The cyclopentadiene type epoxy resin (a) represented by the general formula (1) is obtained by epoxidizing a condensate of dicyclopentadiene. In the above formula, 1 is an integer of 1 or more on the average for heat resistance. It is preferable from the viewpoint of improvement. ) Manufacturing. Since the cyclopentadiene type epoxy resin (a) has a chemical structure in which a dicyclopentadienelene group, which is an aliphatic cyclic skeleton, is polyadded with phenol without passing through a methylene group, the epoxy resin has a large epoxy group equivalent weight. Even if the cured product has a three-dimensional structure with a low crosslink density, heat resistance is maintained because of the rigidity of the main chain skeleton. In addition, the hydrophobicity of the aliphatic cyclic skeleton and the low hydroxyl group concentration of the cured resin make it possible to impart high heat resistance and low water absorption to the cured resin in a well-balanced manner. Therefore, it is an essential epoxy resin as a resin for a printed circuit laminate for a semiconductor package. That is, the water-absorbing property of the epoxy resin cured product cured with the phenol resin has a correlation with the hydroxyl group concentration of the secondary alcohol generated by the reaction of the polar group (epoxy group and phenolic hydroxyl group) of the cured product. In order to reduce water absorption, it is necessary to lower the hydroxyl group concentration of the secondary alcohol. However, lowering the hydroxyl group concentration lowers the crosslink density of the cured product and lowers the heat resistance. The problem of achieving both the low crosslink density and the high heat resistance, which are contradictory properties, can be solved by using the above-mentioned cyclopentadiene-type epoxy resin (a).

The above tetrabromobisphenol A (b)
As the phenolic resin (c) other than the above, those containing three or more phenolic hydroxyl groups are preferable.
Terpene phenol novolak or triphenol methane type phenol is used. The epoxy resin cured with the phenol resin (c) does not hydrolyze even under high temperature and high humidity conditions and has high moisture resistance, and phenol resin is an essential curing agent. The cured product of the resin composition for a printed circuit laminate having only two or less phenolic hydroxyl groups in the molecule has a reduced crosslink density and reduced heat resistance,
Unsatisfactory characteristics cannot be obtained as a printed circuit laminate, which is not preferable.

In particular, novolak of bisphenol A represented by the above formula (2) is preferable from the viewpoint of the balance of properties and cost of the printed circuit laminate. The novolak of bisphenol A is YLH129 (trade name: Yuka Shell Epoxy Co., Ltd.), LF4711 (trade name: Dainippon Ink and Chemicals, Inc.) or LF4871 (trade name: Dainippon Ink and Chemicals, Inc.) Is raised. From the viewpoint of heat resistance, a triphenylmethane-type phenol resin represented by the general formula (3) is preferable. As the triphenylmethane type phenol resin, for example, YL6
065 (trade name: Yuka Shell Epoxy Co., Ltd.). A cured resin using a triphenylmethane-type phenol resin has a high crosslink density and improved heat resistance. Further, terpene phenol novolak is preferred from the viewpoint of adhesive strength and moisture resistance. Examples of the terpene phenol novolak include MP402 represented by the above general formula (4).
{Product name: Yuka Shell Epoxy Co., Ltd.}. Introducing a terpene skeleton having an aliphatic cyclic structure into a phenol resin, like the cyclopentadiene-type epoxy resin, retains heat resistance due to the rigid structure and hydrophobicity of the terpene skeleton, and enables low water absorption.

The curing catalyst (d) is not particularly limited as long as it has the effect of accelerating the reaction between the epoxy group and the phenolic hydroxyl group. For example, tris (dimethylaminomethyl) phenol, dimethylbenzylamine or 1,8-diazabicyclo Tertiary amines such as (5,4,0) undecene-7, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Imidazole compounds such as ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole or 1-isobutyl-2-methylimidazole, tetraethylammonium Bromide, tetraeth Ammonium chloride, tetrapropyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tributyl ammonium chloride, and benzyl tributyl ammonium bromide or phenyl trimethyl ammonium chloride 4
Quaternary ammonium salts, borate salts such as tetraethylammonium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, methyltributylphosphonium tetraphenylborate or tetraphenylphosphonium tetraphenylborate, triphenylphosphine, etc. And boron trifluoride amine complexes such as boron trifluoride monoethylamine. Among these, imidazole compounds are preferred from the viewpoint of promoting the reaction between the epoxy group and the phenolic hydroxyl group and improving the properties of the cured resin. The mixing ratio of the curing catalyst that promotes the reaction between the epoxy group and the phenolic hydroxyl group is from 0.01 to the total amount of the resin composition.
Preferably it is 0.50 weight percent. 0.01
If the amount is less than the weight percentage, a sufficient reaction promoting effect cannot be obtained. On the other hand, when the content exceeds 0.5% by weight, the reaction is so fast that it becomes difficult to control the fluidity of the resin in the case of a prepreg for a printed circuit laminate. Further, the storage stability of the prepreg is deteriorated and the pot life is shortened.

Although it is possible to add a polyfunctional epoxy resin for improving the heat resistance of the resin composition for printed circuits of the present invention, the heat resistance, the adhesive strength, the moisture resistance and the solder heat resistance are generally inferior. These characteristics are inversely proportional, and when the heat resistance is improved, these characteristics are deteriorated. As a result of examining various polyfunctional epoxy resins, it was found that the polyfunctional epoxy resin (e) represented by the above chemical formula (5) has heat resistance without deteriorating the properties of the printed circuit laminate such as adhesive strength, solder heat resistance and moisture resistance. It is possible to improve the performance. As the polyfunctional epoxy resin (e) represented by the chemical formula (5),
VG3101 (trade name: manufactured by Mitsui Chemicals, Inc.). When a polyfunctional epoxy resin other than the one represented by the chemical formula (5) is added, heat resistance is improved, but adhesive strength and solder heat resistance are significantly reduced.

FIGS. 7, 8, 9 and 10 show the cured product of the printed circuit resin composition according to the blending amount of the polyfunctional epoxy resin (e) in the printed circuit resin compositions shown in the following examples, respectively. Glass transition temperature, interlayer adhesion strength,
FIG. 4 is a characteristic diagram showing changes in a water absorption rate and a solder heat resistance test pass rate. The figure shows the printed circuit resin compositions using various phenolic resins (c) by black squares, black circles, and black triangles, respectively. From the figure, it can be seen that the adhesive strength and the solder heat resistance deteriorate when the blending amount of the polyfunctional epoxy resin (e) exceeds 23% by weight, and the polyfunctional epoxy resin (e)
The glass transition temperature, which is an index of heat resistance, increases with the amount of the compound, but the water absorption increases. This glass transition temperature,
From the correlation between the adhesive strength, water absorption and solder heat resistance and the amount of the polyfunctional epoxy resin (e), the polyfunctional epoxy resin to be added in order to have sufficient properties as a printed circuit laminate for a semiconductor package. The amount of (e) is preferably 10 to 23% by weight of the entire resin composition. If the amount is less than 10% by weight of the whole resin composition, the heat resistance will not be improved, and if it exceeds 23% by weight, the heat resistance will be improved but the moisture resistance and the adhesive strength will be reduced.

The printed circuit laminate according to the second embodiment of the present invention is obtained by dissolving the resin composition for a printed circuit in a solvent and applying it to a predetermined base material as a varnish having a predetermined concentration.
It is manufactured by heating and drying after impregnation. The solvent used here is not particularly limited as long as the printed circuit resin composition is dissolved, and examples thereof include alcohols such as ethyl alcohol and propyl alcohol, aromatic hydrocarbons such as toluene and xylene, acetone, Ketones such as methyl ethyl ketone or methyl isobutyl ketone, or ethylene glycol monomethyl ether,
Ethers such as ethylene glycol monoethyl ether or propylene glycol monomethyl ether propylene glycol monoethyl ether are exemplified. The substrate used here is not particularly limited as long as it can be impregnated with the resin composition for printed circuits. Generally, cloths are widely used, but nonwoven fabrics can be used as well. Various glass, aromatic polyamide, liquid crystal polymer, or the like can be used as a material for these substrates.

That is, the resin composition for a printed circuit is dissolved in a solvent, coated and impregnated as a varnish of a predetermined concentration on a predetermined substrate, and heated and dried at 80 to 180 ° C. for 3 to 20 minutes to obtain a prepreg for a printed circuit. I do. The obtained prepreg is cut into a predetermined shape, a predetermined number of the prepregs are laminated, and a copper foil as a conductive layer is heated and pressed in a state of being laminated on at least one surface to obtain a printed circuit laminate. Also, the copper foil is patterned to provide predetermined wiring. The conditions shown here are desirable values, but are not limited thereto.

The laminated board for a multilayer printed circuit according to the third embodiment of the present invention uses the laminated board for a printed circuit provided with the above-mentioned predetermined wiring as a supporting substrate, and an insulating layer and a conductor layer are formed on the supporting substrate. It is manufactured by a build-up method in which a plurality of layers are stacked one by one in order and the layers are sequentially connected. As a method of forming a via hole for connecting between layers of a multilayer printed circuit laminate manufactured by a build-up method, any of a formation method using a photo via, a laser via, plasma, and a sand blast can be used. For the interlayer connection of the via hole, a method using plating and a conductive paste can be used. The insulating layer is made of a thermosetting or thermoplastic resin, and may be in the form of a liquid, a paste, or a film. For the outer layer circuit, plating, a method of laminating a copper foil with resin, a method of bonding the copper foil by heating and pressing, and the like are used. In any of the manufacturing methods and constituent materials, it is possible to manufacture a multilayer printed circuit laminate by a build-up method using the printed circuit laminate as a supporting substrate.

In the semiconductor device according to the fourth embodiment of the present invention, a semiconductor element is mounted on one surface of the printed circuit laminate or the multilayer printed circuit laminate manufactured by the build-up method, and the other is mounted. It is manufactured by forming solder balls in a grid on the surface. Although there is no particular limitation on the method of manufacturing the semiconductor device, as a method of mounting the semiconductor element, the semiconductor element is fixed on the printed circuit board with a silver paste or a ferm adhesive, and is electrically connected to the printed circuit board by wire bonding. Examples of the method include a method of connection and a method of fixing the semiconductor device or the printed circuit laminate to the printed circuit laminate by a protruding electrode and simultaneously performing electrical connection. After mounting the semiconductor element on the printed circuit laminate, the semiconductor element is sealed with a resin to protect the semiconductor element. Examples of the sealing method include a method using a transfer molding machine, a method using dispensing, and a method using printing.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. The present invention is not limited to these examples. The abbreviations of the epoxy resin (a), tetrabromobisphenol A (b), phenol resin (c), and curing catalyst (d) used in the examples and comparative examples are as follows. <Epoxy resin> HP7200H: cyclopentadiene type epoxy resin (epoxy group equivalent: 287) {trade name: HP7200H,
E828: Bisphenol A type epoxy resin (epoxy group equivalent 190) {trade name E828, manufactured by Yuka Shell Epoxy Co., Ltd.} E1001: Bisphenol A type epoxy resin (epoxy group equivalent 470)} Product name: E1001, manufactured by Yuka Shell Epoxy Co., Ltd. BREN-S: heat-resistant and flame-retardant epoxy resin (epoxy group equivalent: 284) Product name: BREN-S, Nippon Kayaku Co., Ltd.
Ｅ E153: Tetrabromobisphenol A type epoxy resin (epoxy group equivalent 401) ｛Product name: EPICLON
153, manufactured by Dainippon Ink Industries, Ltd.)｝ <Polyfunctional epoxy resin> VG3101: Polyfunctional epoxy resin (epoxy group equivalent 2)
11) << Trade name: VG3101, manufactured by Mitsui Chemicals, Inc. >> E157: Bisphenol A novolak type polyfunctional epoxy resin (epoxy group equivalent 207) >> Trade name: E157,
E1032: Triphenylmethane type polyfunctional epoxy resin (epoxy group equivalent: 174) ｛Product name: E1032, manufactured by Yuka Shell Epoxy Co.｝ EOCN104S: Cresol novolac type polyfunctional epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) Epoxy group equivalent 216) ｛Product name: EOCN
104S, manufactured by Nippon Kayaku Co., Ltd. <Tetrabromobisphenol A> TBBA: Tetrabromobisphenol A (phenolic hydroxyl equivalent: 272) {manufactured by Tokyo Chemical Industry Co., Ltd.><Phenolicresin> NHN: Naphthalenephenol novolak (phenolic hydroxyl group) Equivalent 142) ｛Product name: Kayahard NHN, manufactured by Nippon Kayaku Co., Ltd.｝ VR9315: Phenol novolak (phenolic hydroxyl group equivalent 106) ｛Product name: VR9315, manufactured by Mitsui Chemicals, Inc.｝ YLH753: Cresol novolac (phenolic hydroxyl group) Equivalent 118) ｛Product name: YLH
753, manufactured by Yuka Shell Epoxy Co., Ltd. YLH129: Novolak of bisphenol A (two kinds of softening temperatures of 111 ° C. and 125 ° C.) (phenolic hydroxyl equivalent: 120) ｛Product name: YLH129, manufactured by Yuka Shell Epoxy Co., Ltd. ｝ YL6065: triphenylmethane type phenol (phenolic hydroxyl equivalent: 98) ｛Trade name: YL6065,
Yuka Shell Epoxy Co., Ltd.｝ MP402: Terpene phenol novolak (phenolic hydroxyl group equivalent 176) ｛Product name: MP402, Yuka Shell Epoxy Co., Ltd.｝ YP90: Terpene phenol (phenolic hydroxyl equivalent 170) ｛Product name : YP90, manufactured by Yashara Chemical Co., Ltd. DPP-600M: Cyclopentadiene-type phenol (phenolic hydroxyl equivalent: 225) Product name: DPP
-600M, manufactured by Mitsui Chemicals, Inc. <Curing catalyst> 2E4MZ: 2-ethyl-4-methylimidazole {trade name: 2E4MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.><Curing agent other than phenolic resin> DICY: dicyandiamide} Manufactured by Wako Pure Chemical Industries, Ltd.

Embodiment 1 (1) Preparation of Varnish of Resin Composition for Printed Circuit As shown in Table 1, 100 parts by weight of cyclopentadiene type epoxy resin (trade name: HP7200H) (hereinafter referred to as “part”), phenol resin (trade name: Kayahard NHN)
17.8 parts and 60.8 parts of TBBA (tetrabromobisphenol A) were placed in a stirring vessel with a lid, and mixed by stirring to form a uniform solution. Furthermore, a curing catalyst (trade name: 2E4M)
Z) After adding 0.18 parts, the mixture was stirred and mixed to prepare a varnish. In the tables, the amounts are expressed in parts unless otherwise specified.

[0053]

[Table 1]

The varnish was prepared by using a 1: 1 mixed solvent of ethylene glycol monomethyl ether and methyl ethyl ketone as a solvent to have a solid content of 65% by weight. The amount of TBBA is 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

(2) Preparation of Prepreg A varnish of the resin composition for a printed circuit of the above (1) was applied to a 0.1 mm thick glass cloth / cloth style 216:
A prepreg was prepared by coating and impregnating a glass cloth (manufactured by Asahi Schubel Co., Ltd.) or a glass cloth with a thickness of 0.2 mm (Cross Style 7628: manufactured by Asahi Schubel Co., Ltd.), followed by drying by heating at 137 ° C. for 10 minutes.

(3) Molding of Printed Circuit Laminate A predetermined number of prepregs of the above (2) are laminated on both sides with copper foil of 12 μm thickness (manufactured by Furukawa Electric Co., Ltd.), set on a vacuum press and heated. Pressed and molded. Molding conditions are 180
The heating and pressing were performed at 90 ° C. for 90 minutes. After cooling, a sample for measuring the characteristics of the printed circuit laminate, a support substrate for a build-up multilayer printed circuit laminate and a printed circuit laminate for a semiconductor device were prepared.

(4) Measurement of Glass Transition Temperature of Laminated Board for Printed Circuit The thickness of 1.
A 6 mm printed circuit laminate was cut into a size of 8 mm x 8 mm to obtain a glass transition temperature measurement sample, which was measured by a thermomechanical property analyzer TMA. The glass transition temperature was determined by the tangent method, and the results are shown in Table 2.

[0058]

[Table 2]

(5) Measurement of Water Absorption of Printed Circuit Laminate The board thickness of 1.
A 6 mm printed circuit laminate is cut into a 50 mm × 50 mm sample to obtain a water absorption measurement sample, dried in an oven at 125 ° C. for 24 hours, and then dried at 85 ° C., 85% and 121 ° C.
The water absorption was determined from the change in weight when left at 0% and 2 atm for a predetermined time. The water absorption was determined by the following formula, and the results are shown in Table 2. The resin amount of the printed circuit laminate used in the measurement was 43% by weight. Water absorption of printed circuit board [wt%] = [(W2-W1) /
W1] × 100 W1: Weight of printed circuit board after drying W2: Weight of printed circuit board after absorbing water

(6) Measurement of Interlaminar Adhesion Strength of Laminated Board for Printed Circuit The thickness of 1.
25mm x 150mm for 6mm printed circuit laminate
Into a 10 mm wide cut at the center
One prepreg on both sides was peeled off, leaving an m-width portion, to obtain a sample for measuring interlayer adhesive strength. The warp (X) direction was defined as the longitudinal direction. The measurement was carried out according to JIS C6481, and the results are shown in Table 2.

(7) Solder heat resistance test of printed circuit laminates The above-mentioned (3), in which the copper foil on both sides was etched away, was used in a thickness of 0.1 mm.
A 6 mm printed circuit laminate was cut into 50 mm x 50 mm to form a sample for a solder heat resistance test. After drying the sample for soldering heat test in a 125 ° C. oven for 24 hours,
It was boiled in boiling water for 6 hours, taken out after cooling in running water, and wiped off water on the surface to conduct a test. In the solder float test, a test sample after boiling water absorption was floated on molten solder at 300 or 320 ° C. in a solder bath, taken out after 3 minutes, cooled to room temperature, and visually inspected for swelling or peeling. The results are shown in Table 2 as the percentage of the sample that did not swell or peel (pass rate).

(8) Preparation of Laminated Board for Build-up Multilayer Printed Circuit A laminated board for build-up multilayer printed circuit was prepared by the laser via method using the printed circuit laminate of (3) above as a support substrate.

(9) Measurement of water absorption of laminated board for build-up multilayer printed circuit The laminated board for multilayer printed circuit of (8) was 50 mm × 5
The sample was cut into 0 mm to obtain a water absorption measurement sample, dried in an oven at 125 ° C. for 24 hours, and then dried at 85 ° C., 85% and 121%.
The water absorption was determined from the change in weight when left at a temperature of 100 ° C. and 100% for 2 hours. The water absorption was determined by the following calculation formula 1, and the results are shown in Table 3.

[0064]

[Table 3]

The resin content of the printed circuit laminate used as the support substrate of the multilayer printed circuit laminate was 43% by weight.
Met. Water absorption of laminated board for multilayer printed circuit [wt%] = [(W2-W
1) / W1] × 100 W1: Weight of laminated board for multilayer printed circuit after drying W2: Weight of laminated board for multilayer printed circuit after absorbing water

(10) Solder heat resistance test The laminated board for a multilayer printed circuit of the above (8) was subjected to 50 mm × 5
It was cut to 0 mm to obtain a sample for a solder heat resistance test. The sample for the solder heat resistance test was dried in an oven at 125 ° C. for 24 hours, boiled in boiling water for 6 hours, cooled in running water, taken out, and subjected to a surface wiping test. In the solder float test, a test sample after boiling water absorption was floated on molten solder at 288 ° C. and 300 ° C. in a solder bath, taken out after 3 minutes, cooled to room temperature, and visually inspected for swelling or peeling. The results are shown in Table 3 as the percentage of the sample that did not swell or peel (pass rate).

(11) Fabrication of Semiconductor Device The copper foil of the printed circuit laminate of the above (3) is patterned to provide predetermined wiring, and a semiconductor element is die-bonded on the printed circuit laminate with a die bond resin. After connecting the semiconductor element and the printed circuit board by wire bonding, sealing with resin, applying flux to the solder ball pads on the other surface, placing the solder balls, and reflowing to form solder balls Thus, a semiconductor device was manufactured. Further, a semiconductor device was manufactured by connecting to the multilayer printed circuit laminate of the above (8) with the protruding electrode formed on the semiconductor element, sealing with resin, and then forming solder balls on the other surface in the same manner.

(12) Package Crack Resistance Evaluation Test of Semiconductor Device The package crack resistance evaluation test of the semiconductor device is performed by drying the semiconductor device of the above (11) in an oven at 125 ° C. for 24 hours, then at 85 ° C., 65% and 85 ° C. , 85% in a constant temperature and constant temperature bath, passed through an infrared reflow furnace at a maximum temperature of 235 ° C. three times, and checked for cracks in the semiconductor package with a microscope or an ultrasonic microscope. 3 is shown.

(13) Moisture Resistance Evaluation Test of Semiconductor Device The moisture resistance evaluation test of the semiconductor device is performed by drying the semiconductor device of (11) in an oven at 125 ° C. for 24 hours,
A conduction test was conducted to determine whether or not the aluminum wiring of the semiconductor element had broken after being left for a predetermined time under the conditions of ° C., 100%, and 2 atm. In addition, the evaluation of the occurrence of disconnection is indicated by a circle when there is no occurrence of disconnection (0/10) out of 10 samples, and when 1 to 3 disconnections occur (1
３ in case of 3/10), × in case of 4-10 disconnection
Indicated by the mark.

Embodiment 1 2 As shown in Table 1, phenol novolak (trade name: VR9315) was used as the phenol resin of the resin composition varnish for printed circuits instead of NHN, and the composition was 100 parts of cyclopentadiene-type epoxy resin and phenol novolak resin (trade name) : VR9315) 14.0 parts, TBBA
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were produced in the same manner as in Example 1 except that 58.8 parts were used, and the same evaluation test was conducted. The results are shown in Table 2 or 3. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 3 As shown in Table 1, the phenolic resin of the resin composition for printed circuit varnish was cresol novolak (trade name: YLH753) instead of NHN, and was blended with 100 parts of cyclopentadiene-type epoxy resin and cresol novolak resin (trade name). : YLH753) 15.3 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 59.5 parts were used, and the same evaluation test was performed. The results are shown in Table 2 or 3. . The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 4 As shown in Table 1, the phenolic resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 111 ° C.) instead of NHN.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 111 ° C) 15.6 parts, TBBA 59.5
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that the above-mentioned parts were used, and the same evaluation test was conducted. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 5 As shown in Table 1, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 125 ° C) 18.4 parts, TBBA 53.2
A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that the parts were used, and similar evaluation tests were performed. The results are shown in Table 2 or 3. T in the resin composition for a printed circuit of this example
The amount of BBA is 31% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

Embodiment 1 6 As shown in Table 1, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 125 ° C) 15.6 parts, TBBA 59.5
A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that the parts were used, and similar evaluation tests were performed. The results are shown in Table 2 or 3. T in the resin composition for a printed circuit of this example
The amount of BBA was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 7 As shown in Table 1, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 125 ° C) 12.6 parts, TBBA 66.1
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that the above-mentioned parts were used, and the same evaluation test was conducted. The amount of TBBA in the resin composition for printed circuits of this example was 37% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 8 As shown in Table 1, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used instead of NHN for the phenolic resin of the resin composition varnish for printed circuits.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, a softening temperature of 125 ° C.) A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 8.7 parts and 56.0 parts of TBBA were used. The test was performed and the results were listed in Table 2 or 3.
Shown in The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.8.

Embodiment 1 9 As shown in Table 1, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 125 ° C) 12.1 parts, TBBA 57.8
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that the above-mentioned parts were used, and the same evaluation test was conducted. The amount of TBBA in the resin composition for a printed circuit of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.9.

Embodiment 1 10 As shown in Table 1, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used instead of NHN for the phenol resin of the resin composition varnish for printed circuits.
Cyclopentadiene epoxy resin 10
0 parts, bisphenol A novolak (trade name: YLH1)
29, softening temperature 125 ° C) 19.0 parts, TBBA 61.3
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that the above-mentioned parts were used, and the same evaluation test was conducted. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.1.

Embodiment 1 11 As shown in Table 4, the phenol resin of the resin composition varnish for a printed circuit was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of a cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 5.5 parts and 51.9 parts of TBBA were used, and the same evaluation test was performed. 5 and 6.

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

The amount of TBBA in the resin composition for printed circuits of this example was 31% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 12 As shown in Table 4, the phenolic resin of the resin composition varnish for printed circuits was triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A printed circuit board, a multilayer printed circuit board and a semiconductor device were prepared in the same manner as in Example 1 except that 3.1 parts and 58.3 parts of TBBA were used, and the same evaluation test was performed. 5 or 6. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 13 As shown in Table 4, the phenolic resin of the resin composition varnish for printed circuits was prepared by using triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and compounding 100 parts of cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 0.7 part and 65.0 parts of TBBA were used, and the same evaluation test was performed. 5 or 6. The amount of TBBA in the resin composition for printed circuits of this example was 37% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment FIG. 14 As shown in Table 4, the phenol resin of the resin composition varnish for a printed circuit was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of a cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 7.
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 4 parts and 55.4 parts of TBBA were used, and the same evaluation test was performed. Shown in The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.3%.
8

Embodiment 15 As shown in Table 4, the phenolic resin of the resin composition varnish for printed circuits was triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was blended with 100 parts of cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that 0.2 part and 56.9 parts of TBBA were used, and the same evaluation test was performed. Or shown in 6. The amount of TBBA in the resin composition for a printed circuit of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.9.

Embodiment 1 16 As shown in Table 4, the phenolic resin of the resin composition varnish for printed circuits was triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that 6.0 parts and 59.9 parts of TBBA were used, and the same evaluation test was performed. Or shown in 6. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.1.

Embodiment 1 17 As shown in Table 4, terpene phenol novolak (trade name: MP402) was used as the phenol resin of the resin composition varnish for printed circuits instead of NHN, and the composition was 100 parts of cyclopentadiene epoxy resin and terpene phenol novolak (trade name). Name: MP402) 25.0 parts,
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 56.2 parts of TBBA were used, and the same evaluation test was performed. The results are shown in Table 5 or 6. . The amount of TBBA in the resin composition for printed circuits of this example was 31% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment 1 18 As shown in Table 4, the phenol resin of the resin composition varnish for printed circuits was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of a cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 2
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were produced in the same manner as in Example 1 except that 1.0 part and 62.3 parts of TBBA were used, and similar evaluation tests were performed. 5 or 6. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Embodiment. 19 As shown in Table 4, terpene phenol novolak (trade name: MP402) was used in place of NHN as the phenol resin of the resin composition varnish for printed circuits, and 100 parts of cyclopentadiene-type epoxy resin and terpene phenol novolak (trade name) were used. Name: MP402) 16.9 parts,
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were produced in the same manner as in Example 1 except that 68.7 parts of TBBA were used, and the same evaluation test was performed. The results are shown in Table 5 or 6. . The amount of TBBA in the resin composition for printed circuits of this example was 37% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.
0.

Embodiment 1 20 As shown in Table 4, the phenolic resin of the resin composition varnish for printed circuits was replaced with terpene phenol novolak (trade name: MP402) instead of NHN, and was blended with 100 parts of cyclopentadiene type epoxy resin and terpene phenol novolak (trade name). Name: MP402) 11.8 copies,
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that 57.6 parts of TBBA were used, and the same evaluation test was conducted. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.8.

Embodiment 1 21 As shown in Table 4, terpene phenol novolak (trade name: MP402) was used instead of NHN as the phenol resin of the resin composition varnish for printed circuits, and the compounding was 100 parts of cyclopentadiene type epoxy resin and terpene phenol novolak (trade name). Name: MP402) 16.4 parts,
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that the TBBA was 60.0 parts, and the same evaluation test was performed. The results are shown in Table 5 or 6. . The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 0.3%.
9

Embodiment. 22 As shown in Table 4, terpene phenol novolak (trade name: MP402) was used as the phenol resin of the resin composition varnish for printed circuits instead of NHN, and the composition was 100 parts of cyclopentadiene type epoxy resin and terpene phenol novolak (trade name). Name: MP402) 25.6 copies,
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 64.7 parts of TBBA was used, and the same evaluation test was performed. The results are shown in Table 5 or 6. Show. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.
It is one.

Examples 6 and 8 in Tables 1 to 6 above
-10, Example 12, Examples 14-16, Example 18,
Among the evaluation results of the printed circuit laminates of Examples 20 to 22, the ratio of the phenolic hydroxyl group to the epoxy group, the glass transition temperature, the interlayer adhesive strength and the solder heat resistance test pass rate at 320 ° C. FIGS. 1 and 2 collectively show the types of the phenolic resin (c) used in the resin composition.
And the glass transition temperature, the interlayer adhesion strength or 32 according to the ratio of the phenolic hydroxyl group to the epoxy group as shown in FIG.
A characteristic diagram showing a relationship between the solder heat resistance test pass rate at 0 ° C. was obtained. In the figure, YLH129 has a softening point of 125 ° C. As is clear from FIGS. 1 to 3 and Tables 1 to 6, the ratio of the phenolic hydroxyl group to the epoxy group is determined by the glass transition temperature, interlayer adhesion and solder heat resistance, which are the characteristics required for a printed circuit laminate for a semiconductor package. Was found to have a significant effect on Further, the glass transition temperature, the interlayer adhesive strength and the solder heat resistance show the best properties when the ratio of the phenolic hydroxyl group to the epoxy group is around 1.00. For this reason, by setting the ratio of the phenolic hydroxyl group to the epoxy group to 0.98 to 1.02, it is possible to manufacture a highly reliable printed circuit laminate having high glass transition temperature, interlayer adhesive strength and solder heat resistance. Become.

Further, from the evaluation results of the multilayer printed circuit laminate manufactured by the build-up method, the ratio of the phenolic hydroxyl group to the epoxy group was 0.98 to 1.02, using these printed circuit laminates as a support substrate. By doing
It has been found that it is possible to manufacture a highly reliable printed circuit laminate having high solder heat resistance.

The evaluation results of semiconductor devices using these printed circuit laminates and multilayer printed circuit laminates manufactured by a build-up method using the printed circuit laminate as a support substrate also show that the phenolic hydroxyl group and the epoxy group are different. By setting the ratio to 0.98 to 1.02, no package crack occurs in the package crack resistance evaluation test, and no aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs even in the moisture resistance evaluation test. It has been found that a highly reliable semiconductor device can be manufactured.

Embodiment. 23 As shown in Table 7, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used instead of NHN for the phenolic resin of the resin composition varnish for printed circuits.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the blending was carried out with the cyclopentadiene-type epoxy resin 89.4.
Part, polyfunctional epoxy resin (trade name: VG3101) 1
0.6 parts, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 16.8 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that the amount was 60.3 parts, and the same evaluation test was performed. The results are shown in Table 8 or 9. .

[0099]

[Table 7]

[0100]

[Table 8]

[0101]

[Table 9]

The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the amount of polyfunctional epoxy resin (trade name: VG3101) was compounded. The amount is 6 weight percent.

Embodiment 1 24 As shown in Table 7, the phenolic resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the mixture was blended with the cyclopentadiene-type epoxy resin 82.
2 parts, polyfunctional epoxy resin (trade name: VG3101) 1
7.8 parts, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 17.7 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that the amount was 60.7 parts, and the same evaluation test was performed. The results are shown in Table 8 or 9. . The compounding amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the compounding amount of polyfunctional epoxy resin (trade name: VG3101) was 10%. Weight percent.

Embodiment 1 25 As shown in Table 7, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used instead of NHN for the phenolic resin of the resin composition varnish for printed circuits.
And a polyfunctional epoxy resin (trade name: VG3101) in addition to the cyclopentadiene-type epoxy resin.
3 parts, polyfunctional epoxy resin (trade name: VG3101) 3
0.7 parts, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 19.2 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that the amount was 61.5 parts, and the same evaluation test was performed. The results are shown in Table 8 or 9. . The compounding amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the compounding amount of polyfunctional epoxy resin (trade name: VG3101) was 17 Weight percent.

Embodiment 1 26 As shown in Table 7, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used instead of NHN for the phenolic resin of the resin composition varnish for printed circuits.
And a polyfunctional epoxy resin (trade name: VG3101) in addition to the cyclopentadiene-type epoxy resin.
9 parts, polyfunctional epoxy resin (trade name: VG3101) 4
2.1 parts, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 20.7 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that 62.3 parts were used, and the same evaluation test was performed. The results are shown in Table 8 or 9. . The compounding amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the compounding amount of polyfunctional epoxy resin (trade name: VG3101) was 23. Weight percent.

Embodiment 1 27 As shown in Table 7, the phenolic resin of the resin composition varnish for printed circuits was replaced with bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) instead of NHN.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the blending was carried out with the cyclopentadiene-type epoxy resin 50.
2 parts, polyfunctional epoxy resin (trade name: VG3101) 4
9.8 parts, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 21.6 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that the amount was 62.8 parts, and the same evaluation test was performed. The results are shown in Table 8 or 9. . The amount of TBBA in the resin composition for a printed circuit of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the amount of polyfunctional epoxy resin (trade name: VG3101) was 27. Weight percent.

Embodiment 1 28 As shown in Table 7, the phenol resin of the resin composition varnish for printed circuits was a triphenylmethane type phenol (trade name: YL6065) instead of NHN.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the composition was adjusted to 89.6 parts of cyclopentadiene-type epoxy resin, 10.4 parts of polyfunctional epoxy resin (trade name: VG3101), Phenylmethane type phenol (trade name: YL6065)
Example 1 except that 14.2 parts and TBBA 58.9 parts were used.
In the same manner as described above, a printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 8 or 9. The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 6% by weight.

Embodiment 1 29 As shown in Table 7, the phenolic resin of the resin composition varnish for printed circuits was a triphenylmethane type phenol (trade name: YL6065) instead of NHN.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the composition was adjusted to 82.6 parts of cyclopentadiene-type epoxy resin, 17.4 parts of polyfunctional epoxy resin (trade name: VG3101), Phenylmethane type phenol (trade name: YL6065)
Example 1 except that 14.9 parts and 59.3 parts of TBBA were used.
In the same manner as described above, a printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 8 or 9. The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 10% by weight.

Embodiment. 30 As shown in Table 7, the phenol resin of the resin composition varnish for a printed circuit was a triphenylmethane type phenol (trade name: YL6065) instead of NHN.
In addition to the cyclopentadiene type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the compounding was carried out by mixing 70.0 parts of cyclopentadiene type epoxy resin, 30.3 parts of the polyfunctional epoxy resin (trade name: VG3101), Phenylmethane type phenol (trade name: YL6065)
Example 1 except that 16.2 parts and TBBA 60.0 parts were used.
In the same manner as described above, a printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 8 or 9. The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 17% by weight.

Embodiment 1 31 As shown in Table 7, the phenol resin of the resin composition varnish for printed circuits was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN.
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the compounding ratio was 59.1 parts of cyclopentadiene-type epoxy resin, 40.9 parts of polyfunctional epoxy resin (trade name: VG3101), Phenylmethane type phenol (trade name: YL6065)
Example 1 except that 17.4 parts and TBBA 60.6 parts were used.
In the same manner as described above, a printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 8 or 9. The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The blending amount of 3101) is 23% by weight.

Embodiment 1 32 As shown in Table 7, the phenol resin of the resin composition for printed circuit varnish was replaced with NHP instead of NHN using triphenylmethane type phenol (trade name: YL6065).
In addition to the cyclopentadiene-type epoxy resin, a polyfunctional epoxy resin (trade name: VG3101) was added, and the compounding was performed with 51.6 parts of cyclopentadiene-type epoxy resin, 48.4 parts of the polyfunctional epoxy resin (trade name: VG3101), Phenylmethane type phenol (trade name: YL6065)
Example 1 except for 18.1 parts and 61.0 parts of TBBA
In the same manner as described above, a printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 8 or 9. The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 27% by weight.

Embodiment 1 33 As shown in Table 10, terpene phenol novolak (trade name: MP402) was used as the phenolic resin of the resin composition varnish for printed circuits instead of NHN, and in addition to the cyclopentadiene type epoxy resin, 28.8 parts of cyclopentadiene type epoxy resin, 11.2 parts of polyfunctional epoxy resin (product name: VG3101), and terpene phenol novolak (product name: MP402) 22.
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 8 parts and 63.4 parts of TBBA were used, and the same evaluation test was performed. Or 12

[0113]

[Table 10]

[0114]

[Table 11]

[0115]

[Table 12]

The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and the amount of polyfunctional epoxy resin (trade name: VG3101) was compounded. The amount is 6 weight percent.

Embodiment 1 34 As shown in Table 10, the phenol resin of the resin composition for printed circuit varnish was replaced with a terpene phenol novolak (trade name: MP402) instead of NHN. 81.2 parts of cyclopentadiene-type epoxy resin, 18.8 parts of polyfunctional epoxy resin (brand name: VG3101), and terpene phenol novolak (brand name: MP402)
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 0 part and TBBA were 64.0 parts, and the same evaluation test was performed. Or 12 The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 10% by weight.

Embodiment 1 35 As shown in Table 10, terpene phenol novolak (trade name: MP402) was used as the phenolic resin for the resin composition varnish for printed circuits instead of NHN, and in addition to the cyclopentadiene type epoxy resin, a polyfunctional epoxy resin ( 67.4 parts of cyclopentadiene type epoxy resin, 32.6 parts of polyfunctional epoxy resin (brand name: VG3101), and terpene phenol novolak (brand name: MP402) 26.
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 3 parts and 65.2 parts of TBBA were used, and the same evaluation test was performed. Or 12 The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 17% by weight.

Embodiment 1 36 As shown in Table 10, the phenolic resin of the resin composition for printed circuit varnish was replaced with a terpene phenol novolak (trade name: MP402) instead of NHN. 55.2 parts of cyclopentadiene type epoxy resin, 44.8 parts of polyfunctional epoxy resin (brand name: VG3101), and terpene phenol novolak (brand name: MP402) 28.
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 3 parts and 66.2 parts of TBBA were used, and the same evaluation test was performed. Or 12 The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The blending amount of 3101) is 23% by weight.

Embodiment 1 37 As shown in Table 10, terpene phenol novolak (trade name: MP402) was used as the phenol resin of the resin composition varnish for printed circuits instead of NHN, and in addition to the cyclopentadiene type epoxy resin, a polyfunctional epoxy resin ( 46.9 parts of cyclopentadiene-type epoxy resin, 53.1 parts of polyfunctional epoxy resin (brand name: VG3101), and terpene phenol novolak (brand name: MP402) 29.
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were prepared in the same manner as in Example 1 except that 7 parts and 67.0 parts of TBBA were used, and the same evaluation test was performed. Or 12 The amount of TBBA in the resin composition for a printed circuit of this example was 3
4% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and a polyfunctional epoxy resin (trade name: VG
The amount of 3101) is 27% by weight.

Embodiment. 38 As shown in Table 10, the phenolic resin of the resin composition varnish for printed circuits was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and in addition to the cyclopentadiene-type epoxy resin, a triphenylmethane-type polyfunctional epoxy resin (trade name: E1032) was added, and the compounding was performed by mixing 68.4 parts of the cyclopentadiene-type epoxy resin and the triphenylmethane-type epoxy resin. Functional epoxy resin (trade name: E1032) 31.6
Part, bisphenol A novolak (trade name: YLH12
9, softening temperature 125 ° C) 22.5 parts, TBBA 63.2
A laminated board for a printed circuit, a laminated board for a multilayer printed circuit, and a semiconductor device were produced in the same manner as in Example 1 except that the above-mentioned parts were used, and similar evaluation tests were performed. The results are shown in Table 11 or 12. In the resin composition for a printed circuit of this example, the compounding amount of TBBA was 34% by weight, the ratio of the phenolic hydroxyl group to the epoxy group was 1.0, and the compounding amount of the polyfunctional epoxy resin (trade name: E1032) was 17
Weight percent.

Embodiment. 39 As shown in Table 10, the phenolic resin of the resin composition varnish for printed circuits was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and in addition to the cyclopentadiene-type epoxy resin, a cresol novolak-type polyfunctional epoxy resin (trade name: EOCN104S) was added. Resin (trade name: EOCN10)
4S) 30.7 parts, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C) 18.9 parts, T
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 61.4 parts of BBA were used, and the same evaluation test was performed. The results are shown in Table 11 or 12. Show. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and a polyfunctional epoxy resin (trade name: EOCN)
104S) is 17% by weight.

Embodiment. 40 As shown in Table 10, the phenol resin of the resin composition varnish for printed circuits was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was added to the cyclopentadiene-type epoxy resin. Type polyfunctional epoxy resin (trade name: E10
32) was added, and the composition was adjusted to 69.4 parts of cyclopentadiene-type epoxy resin, 30.6 parts of triphenylmethane-type polyfunctional epoxy resin (trade name: E1032), and 18.6 parts of triphenylmethane-type phenol (trade name: YL6065). 8
, A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that 61.3 parts of TBBA were used, and the same evaluation test was performed. Shown in The amount of TBBA in the resin composition for a printed circuit of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and a polyfunctional epoxy resin (trade name: E103)
The amount of 2) is 17% by weight.

Embodiment. 41 As shown in Table 10, a phenol resin of a resin composition varnish for printed circuits was obtained by using triphenylmethane type phenol (trade name: YL6065) instead of NHN, and adding a cresol novolac type to a cyclopentadiene type epoxy resin. Multifunctional epoxy resin (trade name: EO
CN104S) was added, and the mixture was mixed with 70.1 parts of a cyclopentadiene-type epoxy resin and 29.9 parts of a cresol novolak-type polyfunctional epoxy resin (trade name: EOCN104S).
Part, triphenylmethane type phenol (trade name: YL6
065) A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 15.9 parts and 59.8 parts of TBBA were used, and similar evaluation tests were performed. The results are shown in Table 11 or 12.
TBBA in Resin Composition for Printed Circuit of Example
Is 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0, and the amount of polyfunctional epoxy resin (trade name: EOCN104S) is 17% by weight.

Embodiment. 42 As shown in Table 10, terpene phenol novolak (trade name: MP402) was used as the phenolic resin for the resin composition varnish for printed circuits instead of NHN. Functional epoxy resin (trade name: E1032)
Is added, and the composition is changed to cyclopentadiene type epoxy resin 6
6.2 parts, triphenylmethane type polyfunctional epoxy resin (trade name: E1032) 33.8 parts, terpene phenol novolak (trade name: MP402) 31.0 parts, TB
The same procedure as in Example 1 was carried out except that BA was 67.6 parts.
Printed circuit laminates, multilayer printed circuit laminates, and semiconductor devices were produced, and similar evaluation tests were performed. The results are shown in Tables 11 and 12. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.
0, and a polyfunctional epoxy resin (trade name: E103)
The amount of 2) is 17% by weight.

Embodiment. 43 As shown in Table 10, terpene phenol novolak (trade name: MP402) was used as the phenolic resin of the resin composition varnish for printed circuits instead of NHN, and in addition to the cyclopentadiene-type epoxy resin, a cresol novolak-type polyfunctional resin was used. Epoxy resin (trade name: EOCN1)
04S), and blended with 67.6 parts of cyclopentadiene type epoxy resin, 32.4 parts of cresol novolak type polyfunctional epoxy resin (trade name: EOCN104S), and terpene phenol novolak (trade name: MP402) 2
A laminate for a printed circuit, a laminate for a multilayer printed circuit, and a semiconductor device were produced in the same manner as in Example 1 except that 5.8 parts and 64.9 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 11 or 12. The amount of TBBA in the resin composition for printed circuits of this example was 34% by weight, the ratio of phenolic hydroxyl groups to epoxy groups was 1.0, and a polyfunctional epoxy resin (trade name: E
The amount of OCN104S) is 17% by weight.

Examples 6 and 12 in Tables 1 to 12 above
18. Among the evaluation results of the printed circuit laminates of Examples 23 to 43, the compounding amount of the polyfunctional epoxy resin (e), the glass transition temperature, the interlayer adhesive strength, the water absorption, and the solder heat resistance test pass rate were respectively determined. FIGS. 7 and 8 collectively show the types of the phenolic resin (c) used in the resin composition for a printed circuit.
As shown in FIGS. 9 and 10, changes in the glass transition temperature, interlayer adhesion strength, water absorption, and solder heat resistance test pass rate of the cured resin composition for a printed circuit depending on the blending amount of the polyfunctional epoxy resin (e) are shown. The characteristic diagram shown was obtained. In the drawing, YLH129 has a softening point of 125 ° C. FIG.
10 and Tables 1 to 12, the adhesive strength and the solder heat resistance deteriorate when the compounding amount of the polyfunctional epoxy resin (e) exceeds 23% by weight.
It was found that the glass transition temperature, which is an index of heat resistance, increased with the amount of the polyfunctional epoxy resin (e), but the water absorption increased. When a triphenylmethane-type polyfunctional epoxy resin (trade name: E1032) or a cresol novolac-type polyfunctional epoxy resin (trade name: EOCN104S), which is a polyfunctional epoxy resin from the above table, is added, any phenol curing agent is used. Also in the system, it can be seen that the glass transition temperature is improved, but the interlayer adhesion and the solder heat resistance are greatly reduced. However, by using VG3101 as a polyfunctional epoxy resin, it is possible to improve the glass transition temperature without deteriorating properties such as adhesive strength, solder heat resistance, and moisture resistance, and to achieve high heat resistance and high reliability. It turned out that the manufacture of the laminated board for printed circuits was attained. The blending amount of the polyfunctional epoxy resin VG3101 is set to 10 to 23% by weight of the whole resin composition. If the amount of VG3101 is less than 10% by weight of the entire resin composition, the heat resistance will not be improved, and if it exceeds 23% by weight, the heat resistance will be improved but the moisture resistance and the adhesive strength will be reduced.

Further, these printed circuit laminates are used as a support substrate, and a multilayer printed circuit laminate manufactured by a build-up method is also used as a multifunctional epoxy resin.
By using G3101, solder heat resistance is high,
It is possible to manufacture a highly reliable multilayer printed circuit board.

In the semiconductor device using the printed circuit laminate and the multilayer printed circuit laminate manufactured by the build-up method using the printed circuit laminate as a supporting substrate, the VG3101 is used as the polyfunctional epoxy resin. In addition, a package crack does not occur in a package crack resistance evaluation test, and aluminum corrosion breakage of a semiconductor element due to moisture absorption does not occur in a moisture resistance evaluation test, and a highly reliable semiconductor device can be manufactured.

Comparative example. 1 As shown in Table 13, the phenolic resin of the resin composition for printed circuit varnish was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and blended with 100 parts of cyclopentadiene epoxy resin, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 24.5 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 39.3 parts were used, and the same evaluation test was performed. The results are shown in Table 14 or 15. .

[0131]

[Table 13]

[0132]

[Table 14]

[0133]

[Table 15]

The amount of TBBA in the resin composition for printed circuits of this comparative example was 24% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Comparative example. 2 As shown in Table 13, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and blended with 100 parts of cyclopentadiene epoxy resin, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 20.2 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 49.1 parts were used, and the same evaluation test was performed. The results are shown in Table 14 or 15. . The compounding amount of TBBA in the resin composition for a printed circuit of this comparative example was 29% by weight, and the ratio of the phenolic hydroxyl group to the epoxy group was 1.0.

Comparative example. 3 As shown in Table 13, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and blended with 100 parts of cyclopentadiene epoxy resin, bisphenol A novolak (trade name: YL)
H129, softening temperature 125 ° C) 10.6 parts, TBBA
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that the amount was changed to 70.7 parts, and the same evaluation test was performed. The results are shown in Table 14 or 15. . The amount of TBBA in the resin composition for printed circuits of this comparative example was 39% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Comparative example. 4 As shown in Table 13, the phenolic resin of the resin composition for printed circuit varnish was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was mixed with 100 parts of a cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 2
A printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1 except that 0.4 parts and 38.0 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 14 or 15. The compounding amount of TBBA in the resin composition for printed circuits of this comparative example was 24% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Comparative example. 5 As shown in Table 13, the phenol resin of the resin composition varnish for a printed circuit was a triphenylmethane type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of cyclopentadiene type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065) 1
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were manufactured in the same manner as in Example 1 except that 6.9 parts and 47.8 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 14 or 15. The compounding amount of TBBA in the resin composition for a printed circuit of this comparative example was 29% by weight, and the ratio of the phenolic hydroxyl group to the epoxy group was 1.0.

Comparative example. 6 As shown in Table 13, the phenolic resin of the resin composition varnish for printed circuits was a triphenylmethane-type phenol (trade name: YL6065) instead of NHN, and was compounded with 100 parts of cyclopentadiene-type epoxy resin and triphenylmethane. Type phenol (trade name: YL6065)
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 9.0 parts and 69.7 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 14 or 15. The amount of TBBA in the resin composition for printed circuits of this comparative example was 39% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

Comparative example. 7 As shown in Table 13, the phenolic resin of the resin composition varnish for printed circuits was replaced with terpene phenol novolak (trade name: MP402) instead of NHN, and was blended with 100 parts of cyclopentadiene epoxy resin and terpene phenol novolak (trade name) Name: MP402) 34.0
Parts, TBBA 42.3 parts, a printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1, and the same evaluation test was performed. FIG. The amount of TBBA in the resin composition for a printed circuit of this comparative example was 24.
By weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

Comparative example. 8 As shown in Table 13, the phenolic resin of the resin composition varnish for printed circuits was replaced with terpene phenol novolak (trade name: MP402) instead of NHN, and was blended with 100 parts of cyclopentadiene epoxy resin and terpene phenol novolak (trade name) Name: MP402) 27.6
, A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that 52.1 parts of TBBA were used, and the same evaluation test was performed. FIG. The compounding amount of TBBA in the printed circuit resin composition of this comparative example was 29.
By weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

Comparative example. 9 As shown in Table 13, the phenolic resin of the resin composition varnish for printed circuits was replaced with terpene phenol novolak (trade name: MP402) instead of NHN, and was compounded with 100 parts of cyclopentadiene epoxy resin and terpene phenol novolak (trade name) Name: MP402) 14.1
Part, TBBA 73.0 parts, a printed circuit laminate, a multilayer printed circuit laminate and a semiconductor device were prepared in the same manner as in Example 1, and the same evaluation test was performed. FIG. The amount of TBBA in the resin composition for printed circuits of this comparative example was 39.
By weight, the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

Of the evaluation results of the printed circuit laminates of Examples 5 to 7, Examples 11 to 13, Examples 17 to 19, and Comparative Examples 1 to 9 in Tables 1 to 6 and Tables 13 to 15, T
BBA content, glass transition temperature, interlayer adhesion strength and 3
The passing rate of the solder heat resistance test at 20 ° C. is summarized by the type of the phenolic resin (c) used in each resin composition for a printed circuit, and the TBB as shown in FIG. 4, FIG. 5 and FIG.
Glass transition temperature, interlayer adhesive strength and 3 depending on the amount of A
A characteristic diagram showing the relationship between the solder heat resistance test pass rate at 20 ° C. was obtained. In the figure, YHL129 has a softening point of 125 ° C. FIG. 4, FIG. 5, FIG. 6, Tables 1 to 6, Tables 13 to 15
As is clear from the above, the amount of TBBA greatly affects the interlayer adhesion, solder heat resistance, and heat resistance required for a printed circuit laminate for a semiconductor package. The properties of the interlayer adhesive strength and the solder heat resistance are improved up to around 34% by weight together with the amount of TBBA, and thereafter become saturated and show almost constant values. Further, the glass transition temperature, which is an index of heat resistance, decreases with the amount of TBBA because TBBA has only two phenolic hydroxyl groups in the molecule. From the correlation between the adhesive strength, the solder heat resistance, the glass transition temperature and the TBBA content, in order to provide sufficient characteristics as a printed circuit laminate for a semiconductor package, the content of TBBA must be adjusted to 30% of the entire resin composition. It has been found necessary to be ~ 38 weight percent. When the amount is less than 30% by weight (Comparative Examples 1, 2, 4, 5, 7, and 8), the interlayer adhesion of 1.0 kgf / cm or more, which is a measure of the adhesive strength required for a printed circuit laminate for a semiconductor package. The strength is not increased, and the soldering heat resistance is not preferable because the pass rate is not more than half at 320 ° C. When the amount of TBBA exceeds 38% by weight of the whole resin composition (Comparative Examples 3, 6, and 9), the crosslinking density of the cured product is reduced because TBBA has only two phenolic hydroxyl groups in the molecule, and the glass is reduced. The transition temperature drops below 160 ° C.

In addition, in the laminate for a multilayer printed circuit manufactured by the build-up method, the blending amount of TBBA is set to 30 to 38% by weight of the whole resin composition. By
Although it is possible to manufacture a multilayer printed circuit laminate having high soldering heat resistance and high reliability, if less than 30% by weight or more than 38% by weight, the soldering heat resistance is lowered, and a multilayer printed circuit board is reduced. The reliability of the device decreases.

In these printed circuit laminates and in semiconductor devices using multilayer printed circuit laminates manufactured by the build-up method using the printed circuit laminate as a supporting substrate, the amount of TBBA to be added to the resin composition as a whole is 30
By setting the content to about 38% by weight, no package crack occurs in the package crack resistance evaluation test,
Further, even in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption does not occur, and a highly reliable semiconductor device can be manufactured. However, if less than 30% by weight or more than 38% by weight, reflow occurs. Crack resistance and moisture resistance are reduced, and reliability of the semiconductor device is reduced.

Comparative example. 10 As shown in Table 13, bisphenol A novolak type polyfunctional epoxy resin (trade name: E157) was used instead of cyclopentadiene type epoxy resin instead of cyclopentadiene type epoxy resin, and the phenol resin was NHN. Instead, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C.) was used, and 100 parts of bisphenol A novolak type polyfunctional epoxy resin (trade name: E157) and bisphenol A novolak (trade name: YLH129, softening temperature) were used. 125 ° C) 2
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 8.7 parts and 66.4 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 14 or 15. The amount of TBBA in the resin composition for a printed circuit of this comparative example was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above-mentioned resin composition for a printed circuit,
Since bisphenol A novolak type polyfunctional epoxy resin (trade name: E157) was used instead of cyclopentadiene type epoxy resin, the amount of TBBA was 3
4% by weight, despite the ratio of phenolic hydroxyl group to epoxy group being 1.0, the interlayer adhesion strength was lower than that of Examples 1-4, Example 6, Example 12 or Example 18, The water absorption increases, and the reliability of the printed circuit board decreases. Also, in a multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate, solder heat resistance is reduced, and the reliability of the multilayer printed circuit laminate is also reduced. In the package crack resistance evaluation test of the printed circuit laminate or the semiconductor device manufactured using the multilayer printed circuit laminate manufactured by the build-up method using the printed circuit laminate as a supporting substrate, a package crack may occur. In addition, the reflow crack resistance is low, and the reliability of the semiconductor device is low. Furthermore, in this printed circuit laminate and a multilayer printed circuit laminate manufactured by a build-up method using the printed circuit laminate as a support substrate, aluminum corrosion breakage due to moisture absorption occurs in the moisture resistance evaluation test, resulting in low moisture resistance. However, the reliability of the semiconductor device has been reduced. A semiconductor device manufactured using this printed circuit laminate or a multilayer printed circuit laminate manufactured by a build-up method using the printed circuit laminate as a support substrate generates a package crack in a package crack resistance evaluation test, Also in the humidity resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is reduced.

Comparative example. 11 As shown in Table 13, the epoxy resin of the resin composition varnish for printed circuits was replaced by a triphenylmethane-type polyfunctional epoxy resin (trade name: E1032) and a bisphenol A-type epoxy resin instead of using cyclopentadiene-type epoxy resin. (Trade name: E828), and bisphenol A novolak (trade name: YLH129, softening temperature: 125 ° C.) instead of NHN as the phenol resin, and a triphenylmethane-type polyfunctional epoxy resin (trade name: E1032) 50 parts and bisphenol A
Printed circuit in the same manner as in Example 1 except that 50 parts of a type epoxy resin (trade name: E828), 34.5 parts of bisphenol A novolak (trade name: YLH129, softening temperature: 125 ° C.), and 71.5 parts of TBBA were used. A laminated board for multilayer, a laminated board for multilayer printed circuit and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 14 or 15. TB in Printed Circuit Resin Composition of Comparative Example
The amount of BA was 34% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above-mentioned resin composition for a printed circuit,
Instead of using cyclopentadiene type epoxy resin, instead of using triphenylmethane type polyfunctional epoxy resin (trade name: E1
032) and bisphenol A type epoxy resin (trade name: E828), so that the blending amount of TBBA was 34% by weight and the ratio of phenolic hydroxyl group to epoxy group was 1.0. Example 1
4. Compared with Examples 6, 12, and 18, the interlayer adhesive strength is reduced, the amount of water absorption is increased, and the reliability of the printed circuit laminate is reduced. Also, a multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate has low solder heat resistance, and the reliability of the multilayer printed circuit laminate is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 12 As shown in Table 16, the phenol resin of the resin composition varnish for printed circuits was replaced with bisphenol A instead of NHN.
Novolak (trade name: YLH129, softening temperature 125)
° C), and in addition to the cyclopentadiene-type epoxy resin, a tetrabromobisphenol A-type epoxy resin (trade name: EPICLON153) was added, and the compounding was performed with 43.8 parts of cyclopentadiene-type epoxy resin and tetrabromobisphenol A-type epoxy resin. Resin (trade name: EPI
CLON153) 56.2 parts, bisphenol A novolak (trade name: YLH129, softening temperature 125 ° C) 3
A laminated board for printed circuit, a laminated board for multilayer printed circuit and a semiconductor device were prepared in the same manner as in Example 1 except that 5.1 parts and 39.3 parts of TBBA were used, and the same evaluation test was performed. It is shown in Table 17 or 18.

[0151]

[Table 16]

[0152]

[Table 17]

[0153]

[Table 18]

The amount of TBBA in the resin composition for printed circuits of this comparative example was 0% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above resin composition for a printed circuit,
No TBBA was added, and bisphenol A novolak (trade name: YLH129, softening temperature 1) was used as a phenol resin.
25 ° C.) alone, the interlayer adhesive strength and solder heat resistance are lower than those of Examples 1-4, Example 6, Example 12, and Example 18, and the reliability of the printed circuit laminate decreases. ing. In addition, the multilayer board for a multilayer printed circuit manufactured by a build-up method using the printed circuit board as a support substrate also has no TBBA.
The solder heat resistance is reduced, and the reliability of the multilayer printed circuit laminate is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 13 As shown in Table 16, as the phenolic resin of the resin composition varnish for printed circuits, triphenylmethane-type phenol (trade name: YL6065) was used instead of NHN, and tetrabromobisphenol was added to the cyclopentadiene-type epoxy resin. A type epoxy resin (trade name: EP
(ICLON 153), and blended 46.4 parts of a cyclopentadiene type epoxy resin and a tetrabromobisphenol A type epoxy resin (trade name: EPICLON15).
3) In the same manner as in Example 1 except that 53.6 parts, triphenylmethane-type phenol (trade name: YL6065) 24.9 parts, and TBBA 49.1 parts were used, for a printed circuit laminate and a multilayer printed circuit. A laminate and a semiconductor device were manufactured, and the same evaluation test was performed. The results are shown in Table 17 or 18. The compounding amount of TBBA in the resin composition for printed circuits of this comparative example was 0% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above resin composition for a printed circuit,
Since TBBA was not added and only triphenylmethane-type phenol (trade name: YL6065) was used as the phenol resin, Examples 1 to 4, Example 6, Example 12,
Compared with Example 18, the interlayer adhesive strength and the solder heat resistance were low, and the reliability of the printed circuit laminate was reduced. In addition, this printed circuit laminate is used as a support substrate,
Also in the multilayer printed circuit laminate manufactured by the build-up method, since TBBA is not added, the solder heat resistance is low, and the reliability of the multilayer printed circuit laminate is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 14 As shown in Table 16, terpene phenol novolak (trade name: MP402) was used as the phenol resin of the resin composition varnish for printed circuits instead of NHN, and in addition to the cyclopentadiene type epoxy resin, tetrabromobisphenol A type was used. Epoxy resin (trade name: EPICL)
ON153) was added, and the mixture was mixed with 37.4 parts of cyclopentadiene-type epoxy resin and tetrabromobisphenol A.
Type epoxy resin (trade name: EPICLON153) 5
3.6 parts, terpene phenol novolak (trade name: M
P402) A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 50.4 parts and 70.7 parts of TBBA were used, and similar evaluation tests were performed. The results are shown in Table 17 or 18. TB in Printed Circuit Resin Composition of Comparative Example
The amount of BA was 0% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above resin composition for a printed circuit,
Since TBBA was not added and only terpene phenol novolak (trade name: MP402) was used as the phenol resin, the interlayer adhesion strength and solder heat resistance were higher than those of Examples 1-4, Example 6, Example 12, and Example 18. And the reliability of the printed circuit laminate is reduced. In addition, in the case of a multilayer printed circuit laminate manufactured by a build-up method using the printed circuit laminate as a support substrate, the addition of TBBA also reduces the solder heat resistance, and reduces the reliability of the multilayer printed circuit laminate. Is declining. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 15 As shown in Table 16, DICY (dicyandiamide) as an amine curing agent was used in place of NHN of the phenol resin of the resin composition varnish for printed circuits, and bisphenol A was added to the cyclopentadiene type epoxy resin.
Type epoxy resin (trade name: E1001) and heat-resistant flame-retardant epoxy resin (trade name: BREN-S) were added, and the compounding was 50.0 parts of cyclopentadiene type epoxy resin and bisphenol A type epoxy resin (trade name: E1001). 1
0.0 parts, heat-resistant flame-retardant epoxy resin (trade name: BREN-
S) A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that 40 parts and 3.5 parts of DICY (dicyandiamide) were used, and similar evaluation tests were performed. Table 17 or 1
FIG. The resin composition for printed circuits of this comparative example includes:
TBBA and phenolic resins other than TBBA were not added.

In the above resin composition for printed circuits,
Since neither TBBA nor phenolic resins other than TBBA were added and only DICY was used as a curing agent, the amount of water absorption increased as compared with Examples 1 to 4, Example 6, Example 12, and Example 18, and solder heat resistance was increased. And the reliability of the printed circuit laminate is reduced. Also, in a multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate, solder heat resistance is reduced, and the reliability of the multilayer printed circuit laminate is also reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 16 As shown in Table 16, DICY (dicyandiamide) as an amine curing agent was used in place of NHN of the phenol resin of the resin composition varnish for printed circuits, and in addition to the cyclopentadiene-type epoxy resin, a heat-resistant flame-retardant epoxy resin was used. (Trade name: BREN-S), and compounded with 59.0 parts of cyclopentadiene-type epoxy resin, 15 parts of heat-resistant and flame-retardant epoxy resin (trade name: BREN-S),
In the same manner as in Example 1 except that 26 parts and 2.4 parts of DICY (dicyandiamide) were used,
Producing a laminate and a semiconductor device for a multilayer printed circuit,
The same evaluation test was performed, and the results are shown in Tables 17 and 18. T in the resin composition for printed circuits of this comparative example
The amount of BBA is 26% by weight.

In the above resin composition for a printed circuit,
Since no phenolic resin other than TBBA was added and TBBA and DICY were used as curing agents, Examples 1 to 4,
As compared with Examples 6, 12, and 18, the amount of water absorption is increased, the solder heat resistance is low, and the reliability of the printed circuit board is reduced. In addition, the multilayer printed circuit laminate manufactured by the build-up method using the printed circuit laminate as a support substrate also has a low solder heat resistance because the phenol resin is not added and DICY is added. The reliability of the printed circuit board has decreased. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 17 As shown in Table 16, DICY (dicyandiamide) as an amine curing agent was used in place of NHN of the phenol resin of the resin composition varnish for printed circuits, and the compounding was 66.0 parts of a cyclopentadiene-type epoxy resin and TBBA 3
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were produced in the same manner as in Example 1 except that 4 parts and 1.4 parts of DICY (dicyandiamide) were used, and the same evaluation test was performed. Is shown in Table 17 or 18. TB in Printed Circuit Resin Composition of Comparative Example
The amount of BA is 34% by weight.

In the above resin composition for a printed circuit,
Since phenolic resins other than TBBA were not added and TBBA and DICY were used as curing agents, the amount of TBBA was 34% by weight, but Examples 1-4, Example 6, Example 12, and Compared with Example 18, the amount of water absorption was increased, the solder heat resistance was low, and the reliability of the printed circuit board was reduced. Also, the multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate has low solder heat resistance, and the reliability of the multilayer printed circuit laminate is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 18 As shown in Table 16, DICY (dicyandiamide), which is an amine curing agent, was used in place of NHN of the phenol resin of the resin composition varnish for printed circuits, and in addition to the cyclopentadiene type epoxy resin, the triphenylmethane type polyfunctional epoxy resin was used. (Trade name: E1032), and blended with 59.0 parts of cyclopentadiene type epoxy resin and triphenylmethane type polyfunctional epoxy resin (trade name: E10)
32) A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that 10.0 parts, 31 parts of TBBA, and 1.4 parts of DICY (dicyandiamide) were used. The same evaluation test was performed, and the results are shown in Tables 17 and 18. The compounding amount of TBBA in the resin composition for printed circuits of this comparative example is 31% by weight.

In the above-mentioned resin composition for a printed circuit,
Since phenolic resins other than TBBA were not added and TBBA and DICY were used as curing agents, the amount of TBBA was 34% by weight, but Examples 1-4, Example 6, Example 12, and Compared with Example 18, the amount of water absorption was increased, the solder heat resistance was low, and the reliability of the printed circuit board was reduced. Also, the multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate has low solder heat resistance, and the reliability of the multilayer printed circuit laminate is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 19 As shown in Table 16, cyclopentadiene-type phenol (trade name: DPP-600M) was used instead of NHN of the phenol resin of the resin composition varnish for printed circuits,
67.0 parts of cyclopentadiene type epoxy resin,
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1, except that 34 parts of TBBA and 25.3 parts of cyclopentadiene-type phenol (trade name: DPP-600M) were used. The same evaluation test was performed, and the results are shown in Table 17 or 18.
TBBA in Printed Circuit Resin Composition of Comparative Example
Is 26 weight percent and the ratio of phenolic hydroxyl groups to epoxy groups is 1.0.

In the above-mentioned resin composition for a printed circuit,
A cyclopentadiene type epoxy resin, a phenol resin other than TBBA, and TBBA are added.
Since the compounding amount of BA is 26% by weight, the interlayer adhesion and the solder heat resistance are lower than those of Examples 1-4, Example 6, Example 12, and Example 18, and the reliability of the printed circuit board is low. Sex has declined. Also, in the multilayer printed circuit laminate manufactured by the build-up method using the printed circuit laminate as a supporting substrate, the compounding amount of TBBA is 26% by weight. The reliability of the laminate has decreased. A semiconductor device manufactured using this printed circuit laminate or a multilayer printed circuit laminate manufactured by a build-up method using the printed circuit laminate as a support substrate generates a package crack in a package crack resistance evaluation test, Also in the humidity resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is reduced.

Comparative example. 20 As shown in Table 16, instead of NHN of the phenol resin of the resin composition for printed circuit varnish, menthan type phenol (trade name: YP-90) was used, and the compounding was 67.0 parts of cyclopentadiene type epoxy resin, Type phenol (trade name: YP-90) 23.0 parts, TBBA
A printed circuit board, a multilayer printed circuit board, and a semiconductor device were prepared in the same manner as in Example 1 except that the number of parts was 33, and the same evaluation test was performed.
Or 18. The amount of TBBA in the resin composition for printed circuits of this comparative example was 27% by weight, and the ratio of phenolic hydroxyl groups to epoxy groups was 1.0.

In the above-mentioned resin composition for a printed circuit,
Cyclopentadiene type epoxy resin, phenol resin other than TBBA, and TBBA are added.
Is 27% by weight, and in addition to the fact that YP90 has only two phenolic hydroxyl groups in the molecule, Examples 1 to 4, Example 6, Example 12, and Example 1
Compared with No. 8, the glass transition temperature and the solder heat resistance were low, and the reliability of the printed circuit board was low. Also, in the multilayer printed circuit laminate manufactured by the build-up method using the printed circuit laminate as a support substrate, the compounding amount of TBBA is 27% by weight, and YP90 has only two phenolic hydroxyl groups in the molecule. Since it does not have this, the solder heat resistance is reduced, and the reliability of the multilayer board for a multilayer printed circuit is reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 21 As shown in Table 16, as a printed circuit laminate, a commercially available FR-4 grade glass epoxy printed circuit laminate. Product name: CCL-E170, Mitsubishi Gas Chemical Co., Ltd.
In the same manner as in Example 1 to produce a printed circuit board, a multilayer printed circuit board, and a semiconductor device. The same evaluation test was performed.
FIG.

Since the FR-4 grade glass epoxy printed circuit laminate uses DICY as a curing agent, it absorbs more water than Examples 1-4, Examples 6, 12 and 18. The amount is large, the solder heat resistance is low, and the reliability of the printed circuit board is reduced. Also, in the multilayer printed circuit laminate manufactured by a build-up method using the printed circuit laminate as a support substrate, DICY is used as a curing agent, so that the solder heat resistance is low, and the multilayer printed circuit laminate is reduced. Has decreased in reliability. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and Also, in the moisture resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is lowered.

Comparative example. 22 As shown in Table 16, a printed circuit laminate using a commercially available BT resin as the printed circuit laminate.
A printed circuit laminate, a multilayer printed circuit laminate, and a semiconductor device were prepared in the same manner as in Example 1 except that CL-HL830 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used, and similar evaluation tests were performed. The results are shown in Table 17 or 18.

In the above-mentioned resin composition for a printed circuit,
Since the BT resin is used, the interlayer adhesive strength and the solder heat resistance are lower than those of Examples 1 to 4, Example 6, Example 12, and Example 18, and the reliability of the printed circuit laminate decreases. I have. Also, in a multilayer printed circuit laminate manufactured by a build-up method using this printed circuit laminate as a support substrate, solder heat resistance is reduced, and the reliability of the multilayer printed circuit laminate is also reduced. A semiconductor device manufactured using the printed circuit board or a multilayer printed circuit board manufactured by a build-up method using the printed circuit board as a supporting substrate is subject to package cracking in a package crack resistance evaluation test, and ,
Also in the humidity resistance evaluation test, aluminum corrosion breakage of the semiconductor element due to moisture absorption occurs, and the reliability of the semiconductor device is reduced.

[0176]

According to the first resin composition for a printed circuit of the present invention, the cyclopentadiene type epoxy resin (a), tetrabromobisphenol A (b), and tetrabromobisphenol represented by the above general formula (1) are used. A phenolic resin (c) other than A (b) and a curing catalyst (d) that promotes the reaction between an epoxy group and a phenolic hydroxyl group,
The resin composition for a printed circuit in which the amount of the above-mentioned tetrabromobisphenol A (b) is 30 to 38% by weight of the whole composition, and the cured product has heat resistance, moisture resistance, adhesive strength and solder heat resistance. Is effective.

According to the second resin composition for a printed circuit of the present invention, in the first resin composition for a printed circuit, the cyclopentadiene type epoxy resin (a), tetrabromobisphenol A (b) and phenol resin (C) is blended so that the ratio of phenolic hydroxyl group to epoxy group (phenolic hydroxyl group / epoxy group) is 0.98 to 1.02, and a cured product is required for a printed circuit laminate. The heat resistance, moisture resistance, adhesive strength and solder heat resistance.

According to the third resin composition for a printed circuit of the present invention, in the first or second resin composition for a printed circuit, the phenolic resin (c) is a bisphenol represented by the general formula (2). A novolak resin, triphenylmethane type phenol resin represented by the above general formula (3), or terpene phenol novolak resin represented by the above general formula (4), and a cured product is required for a printed circuit laminate. The heat resistance, moisture resistance, adhesive strength and solder heat resistance.

The fourth resin composition for a printed circuit of the present invention is the same as the resin composition for a printed circuit according to any one of the first to third aspects, except that the polyfunctional epoxy resin (e) represented by the chemical formula (5) is used. The composition is blended in an amount of 10 to 23% by weight of the entire composition, and the cured product has the moisture resistance, adhesive strength, and solder heat resistance required for a printed circuit laminate, and the heat resistance is further improved. There is.

The first printed circuit board laminate of the present invention comprises:
A conductive layer is provided on at least one surface of an insulating material impregnated with any of the first to fourth printed circuit resin compositions. The insulating material has high heat resistance, low water absorption, high adhesion, excellent solder heat resistance, and BGA. This has the effect of being suitably used for semiconductor packages such as packages.

The second laminated board for printed circuit of the present invention comprises:
In the first printed circuit laminate, the conductive layer is patterned and has high heat resistance, low water absorption, high adhesion, and excellent solder heat resistance, and is suitably used for semiconductor packages such as BGA packages. This has the effect.

The first multilayer printed circuit laminate of the present invention is obtained by alternately laminating insulating layers and conductor layers in this order on the second printed circuit laminate by the build-up method in this order. It has low water absorption, high adhesiveness, and excellent solder heat resistance, and has the effect of being suitably used for semiconductor packages such as BGA packages.

In the first ball grid array type semiconductor device of the present invention, a semiconductor element is provided on one surface of the second printed circuit laminate or the first multilayer printed circuit laminate, and the other is provided. In which solder balls are formed, which has an effect of high crack resistance and high reliability.

[Brief description of the drawings]

FIG. 1 is a characteristic diagram showing a change in a glass transition temperature of a cured product according to a ratio of a phenolic hydroxyl group to an epoxy group in a resin composition for a printed circuit of the present invention.

FIG. 2 is a characteristic diagram showing a change in an interlayer adhesive strength of a cured product according to a ratio of a phenolic hydroxyl group to an epoxy group in the resin composition for a printed circuit of the present invention.

FIG. 3 is a characteristic diagram showing a change in a solder heat resistance test pass rate of a cured product according to a ratio of a phenolic hydroxyl group to an epoxy group in a printed circuit resin composition of the present invention.

FIG. 4 is a characteristic diagram showing a change in a glass transition temperature of a cured product according to a compounding amount of tetrabromobisphenol A in a resin composition for a printed circuit of the present invention.

FIG. 5 is a characteristic diagram showing a change in interlayer adhesion strength of a cured product according to the amount of tetrabromobisphenol A in the resin composition for a printed circuit of the present invention.

FIG. 6 is a characteristic diagram showing a change in a solder heat resistance test pass rate of a cured product of the resin composition for a printed circuit of the present invention depending on the amount of tetrabromobisphenol A added.

FIG. 7 is a characteristic diagram showing a change in a glass transition temperature of a cured product according to a blending amount of a polyfunctional epoxy resin in a resin composition for a printed circuit of the present invention.

FIG. 8 is a characteristic diagram showing a change in the interlayer adhesion strength of a cured product according to the blending amount of a polyfunctional epoxy resin in the resin composition for a printed circuit of the present invention.

FIG. 9 is a characteristic diagram showing a change in a water absorption of a cured product according to a blending amount of a polyfunctional epoxy resin in a resin composition for a printed circuit of the present invention.

FIG. 10 is a characteristic diagram showing a change in a solder heat resistance test pass rate of a cured product according to a blending amount of a polyfunctional epoxy resin in a resin composition for a printed circuit of the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akihiko Yamaguchi 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsui Electric Co., Ltd. (72) Inventor Kazuo Funabashi 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Rishi Electric Co., Ltd.

Claims (8)

[Claims] [Claim 1] The following general formula (1) (Wherein, l is an integer of 0 to 3 on average), cyclopentadiene-type epoxy resin (a), tetrabromobisphenol A (b), tetrabromobisphenol A
A phenolic resin (c) other than (b) and a curing catalyst (d) for accelerating the reaction between an epoxy group and a phenolic hydroxyl group are blended, and the blending amount of the above tetrabromobisphenol A (b) is 30 to 38 of the whole composition. A resin composition for a printed circuit which is a weight percentage. 2. The cyclopentadiene type epoxy resin (a), the tetrabromobisphenol A (b) and the phenolic resin (c) having a ratio of phenolic hydroxyl group to epoxy group (phenolic hydroxyl group / epoxy group) of 0.98.
The resin composition for a printed circuit according to claim 1, wherein the resin composition is blended so as to be 1.02 to 1.02. 3. A phenol resin (c) having the following general formula (2): (Wherein, m is an integer of 0 to 8 on average) a bisphenol A novolak resin represented by the following general formula (3): Wherein n is an integer of 0 to 5 on average, or a triphenylmethane-type phenol resin represented by the following general formula (4): The resin composition for a printed circuit according to claim 1, wherein the resin composition is a terpene phenol novolak resin represented by the formula (where p is an integer of 0 to 8 on average). 4. Chemical formula (5) The polyfunctional epoxy resin (e) represented by
The resin composition for a printed circuit according to any one of claims 1 to 3, wherein the resin composition is blended in an amount of from 23 to 23% by weight. 5. A printed circuit laminate comprising an insulating material impregnated with the printed circuit resin composition according to claim 1 and a conductive layer provided on at least one surface of the insulating material. 6. The printed circuit board according to claim 5, wherein the conductive layer is patterned. 7. A multilayer printed circuit laminate according to claim 6, wherein insulating layers and conductor layers are alternately laminated on the printed circuit laminate according to the build-up method in this order. 8. A ball grid array type wherein a semiconductor element is provided on one surface of the printed circuit laminate or the multilayer printed circuit laminate according to claim 6 and solder balls are formed on the other surface. Semiconductor device.