JP2011144229A - Cyanate resin composition, prepreg, laminated board, printed wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyanate resin composition that is excellent in light shielding properties while maintaining a high glass transition temperature and excellent soldering heat resistance, and a prepreg, a laminated board, a resin sheet, a printed wiring board, and a semiconductor device using the resin composition. <P>SOLUTION: The cyanate resin composition includes a cyanate resin and a fluorescent dye compound represented by formula (1) as indispensable components, wherein R<SP>1</SP>and R<SP>2</SP>are each hydrogen or a substituent selected from the group consisting of hydroxy, ethyl, methyl, butyl, tertiary butyl, phenyl, and carboxy, and R<SP>1</SP>and R<SP>2</SP>may be the same or different from each other. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a cyanate resin composition, a prepreg, a laminated board, a printed wiring board, and a semiconductor device.

In recent years, with the demand for higher functionality of electronic devices, etc., the integration of electronic components and the mounting of high-density packaging have been progressing. In addition, miniaturization and higher density are progressing.
However, when the printed wiring board is thinned, there arises a problem that mounting reliability is lowered and warping of the printed wiring board is increased.
Therefore, the hardened | cured material of the resin composition used for the insulating layer of a printed wiring board is examined using the cyanate resin composition which has a low coefficient of thermal expansion and has a high glass transition temperature (for example, prior literature 1). .

On the other hand, the solder resist used for the outermost layer of the printed wiring board is usually a photosensitive resin (photoresist) (Cited document 2).
Generally, since a solder resist is a photocurable material, it has a high light transmittance.
Therefore, at the time of manufacturing a printed wiring board, a solder resist was formed on both sides of the laminate, and a circuit exposed part and a covering part were formed. There was a problem that the solder resist was irradiated with light and the solder resist on the other surface was cured. For this reason, the solder resist on the other surface cannot be exposed and developed by a photographic method, and there is a problem that the exposed portion and the covering portion of the conductor circuit cannot be formed in an arbitrary pattern.

In order to solve the above-mentioned problem, a method is considered in which a light-shielding substance is contained in a cyanate resin composition to prevent light from transmitting (for example, cited document 3).

However, the cyanate resin composition has a problem in that performance degradation as a printed wiring board material is caused by including a light shielding substance. For example, when diaminostilbene dyes, fluorescein, thioflavine, and eosin are added to the cyanate resin composition, the light shielding material is separated or the structure is destroyed in the cyanate resin composition, resulting in a decrease in light absorption ability. There was a problem.

JP2009-35728A JP 2009-258613 A JP2002-194226

  The present invention relates to a cyanate resin composition excellent in light shielding properties while maintaining a high glass transition temperature and excellent soldering heat resistance, and a prepreg, a laminate, a resin sheet, and a printed wiring using the resin composition A board and a semiconductor device are provided.

Such an object is achieved by the present invention described in the following items [1] to [8].
[1] A cyanate resin composition comprising a cyanate resin and a compound represented by the following formula (1) as essential components.

(R1 in the formula, and R2 is hydrogen or a hydroxyl group, an ethyl group, a methyl group, butyl group, tertiary butyl group, a phenyl group and a substituent selected from the group consisting of carboxyl group, and R ¹ R ² may be the same as or different from each other.
[2] A prepreg obtained by impregnating a base material with the cyanate resin composition according to the item [1].
[3] A metal-clad laminate having a metal foil on at least one surface of a resin-impregnated substrate layer obtained by impregnating the cyanate resin composition according to the item [1] in a substrate.
[4] A metal-clad laminate obtained by superimposing metal foil on at least one surface of the prepreg according to the item [1] or a laminate in which two or more prepregs are superposed and heating and pressing.
[5] A resin sheet formed by forming a resin layer comprising the cyanate resin composition according to the item [1] on a film or a metal foil.
[6] A printed wiring board comprising the metal-clad laminate according to the item [3] or [4] as an inner circuit board.
[7] Printed wiring board [8] [6] or [7] described in [6], wherein at least one layer of the prepreg described in [2] is laminated on the inner layer circuit board A semiconductor device in which a semiconductor element is mounted on a plate.

The cyanate resin composition of the present invention has a high glass transition temperature, is excellent in solder heat resistance, and is excellent in light shielding properties.

Hereinafter, the cyanate resin composition, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device of the present invention will be described.

The cyanate resin composition of the present invention can be impregnated in a substrate such as a glass fiber substrate and used for a prepreg and a laminate using the prepreg.
Or it can use as a resin sheet formed by laminating | stacking the resin layer which consists of a cyanate resin composition on a film or metal foil.
Moreover, since the cyanate resin composition of this invention has the outstanding insulation, it can be used for the insulating layer of a printed wiring board, for example.
Furthermore, since the cyanate resin composition of the present invention has low linear expansion and is excellent in heat resistance and adhesion to a conductor circuit, it can be used as an interposer for a semiconductor device.

As a printed wiring board of a semiconductor device, a mother board and an interposer are known. The interposer is a printed wiring board similar to the mother board, but is interposed between the semiconductor element (bare chip) or semiconductor package and the mother board and mounted on the mother board.
The interposer may be used as a substrate on which a semiconductor package is mounted in the same manner as a mother board. However, the interposer is used as a package substrate or a module substrate as a specific usage method different from the mother board.

  The package substrate means that an interposer is used as a substrate of a semiconductor package. In a semiconductor package, a semiconductor element is mounted on a lead frame, both are connected by wire bonding and sealed with resin, and an interposer is used as a package substrate, and a semiconductor element is mounted on the interposer, There is a type that is connected by a method such as wire bonding and sealed with resin.

Next, details of the cyanate resin composition of the present invention will be described.
The method described below is not particularly limited, and any known method can be used.

The cyanate resin composition of the present invention contains a cyanate resin and a compound represented by the following general formula (1) as essential components. As a result, a high glass transition temperature can be achieved, and excellent heat resistance and light shielding properties can be achieved.

(R1 in the formula, and R2 is hydrogen or a hydroxyl group, an ethyl group, a methyl group, butyl group, tertiary butyl group, a phenyl group and a substituent selected from the group consisting of carboxyl group, and R ¹ R ² may be the same as or different from each other.

The cyanate resin is not particularly limited. For example, 2,2′-bis (4-cyanatephenyl) propane, 2,2′-bis (4-cyanatephenyl) ethane, and 2,2′-bis (4- Other examples include cyanate-3,5-methylphenyl) ethane, and other cyanate resins described in JP-A-2009-35728. One or two or more may be used as appropriate. These cyanate compounds may be used as they are, or prepolymerized ones can also be used.
In addition, although the method to prepolymerize is not specifically limited, For example, it can obtain by heating to about 50-200 degreeC. Moreover, it can prepolymerize by heating in presence of a catalyst.

Examples of the catalyst include, but are not limited to, acids such as mineral acids and Lewis acids; bases such as sodium alcoholates and tertiary amines; salts such as sodium carbonate; and activities such as bisphenol compounds and monophenol compounds. And hydrogen-containing compounds.

The compound represented by the formula (1) has a stilbene structure, absorbs ultraviolet and visible light, and further has a pyrazoline ring, so that it has excellent colorability and sharpness. Thus, light in the long wavelength region can be shielded. Moreover, heat resistance is improved by shaking the aromatic ring.
Further, there is no problem that the light absorption ability is lowered when the above-mentioned diaminostilbene dye, fluorescein, thioflavine or eosin is used.

R ¹ and R ² in the formula (1) are hydrogen or a substituent selected from the group consisting of a hydroxyl group, an ethyl group, a methyl group, a butyl group, a tertiary butyl group, a phenyl group, and a carboxyl group. R1 and R2 may be the same or different.
R ¹ and R ² can be easily selected by a conventional method when synthesizing the compound represented by the formula (1).
R ¹ and R ² are preferably a tertiary butyl group. Thereby, sufficient curability is expressed, the glass transition temperature is high, the solder heat resistance is excellent, and the light shielding property is excellent.

Although the compounding quantity of the compound represented by said Formula (1) is not specifically limited, 0.01%-1.0% are preferable in 100 weight part of cyanate resin. If the blending amount is less than the lower limit value, the light irradiated on one surface passes through a solder resist (sometimes called a photoresist), further passes through the laminated plate, and the other solder resist is cured. There is a case. Moreover, when larger than the said upper limit, the compound represented by Formula (1) may aggregate and a sufficient light-shielding effect may not be expressed.

In the cyanate resin composition of the present invention, it is preferable to use an epoxy resin in combination in consideration of the balance between characteristics such as heat resistance and moisture resistance and cost.
The epoxy resin is not particularly limited, and for example, bisphenol type epoxy resin, novolak type epoxy resin, aliphatic chain epoxy resin, epoxidized polybutadiene, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and the like are preferably used. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol type epoxy resin such as bisphenol S type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, novolak type epoxy such as salicylaldehyde phenol novolak type epoxy resin A resin is more preferably used. From the viewpoint of improving heat resistance, it is particularly preferable to use a bisphenol A novolak type epoxy resin, a cresol novolak type epoxy resin or a salicylaldehyde phenol novolak type epoxy resin. These resins may be used alone or in combination of two or more.

It is also desirable that the cyanate resin composition of the present invention is used in combination with an accelerator in order to accelerate curing. The type and amount of the accelerator are not particularly limited. For example, an imidazole compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, a metal salt, or the like is used, and two or more types are used in combination. Also good.

The cyanate resin composition of this invention can add additives other than the said component in the range which does not impair a characteristic as needed. Components other than the above components include, for example, epoxy silane coupling agents, cationic silane coupling agents, amino silane coupling agents, titanate coupling agents, silicone oil type coupling agents, etc., silica, aluminum hydroxide Inorganic fillers such as talc, surface conditioners such as acrylic polymers, colorants such as dyes and pigments, flame retardants, and the like.

Next, the prepreg will be described.

The prepreg of the present invention is obtained by impregnating a base material with the above-described cyanate resin composition. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.
Examples of the base material include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, or inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, aromatic polyamide resins, polyamide resins, Examples thereof include organic fiber base materials composed of organic fibers such as aromatic polyester resins, polyester resins, polyimide resins, and fluororesins. Among these base materials, glass fiber base materials represented by glass woven fabric are preferable in terms of strength and water absorption.

Examples of the method of impregnating the base material with the cyanate resin composition include, for example, a method in which a cyanate resin composition is made into a resin varnish using a solvent, the base material is immersed in the resin varnish, a method of applying with various coaters, and a spraying method of spraying Etc. Among these, the method of immersing the base material in the resin varnish is preferable. Thereby, the impregnation property of the resin composition with respect to a base material can be improved. In addition, when a base material is immersed in a resin varnish, a normal impregnation coating equipment can be used.

The solvent used in the resin varnish desirably has good solubility in the cyanate resin composition, but a poor solvent may be used as long as it does not have an adverse effect. Examples of the solvent exhibiting good solubility include N, N-dimethylformamide.
The solid content in the resin varnish is not particularly limited, but the solid content of the cyanate resin composition is preferably 40 to 80% by weight, and particularly preferably 50 to 65% by weight. Thereby, the impregnation property to the base material of a resin varnish can further be improved.
A prepreg can be obtained by impregnating the base material with the cyanate resin composition and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, the resin sheet will be described.

The resin sheet using the cyanate resin composition is obtained by forming an insulating layer made of the resin varnish on a film or a metal foil.

Although content of the cyanate resin composition in the said resin varnish is not specifically limited, 45 to 85 weight% is preferable and 55 to 75 weight% is especially preferable.

Next, the resin varnish is coated on a film or metal foil using various coating apparatuses, and then dried. Or after spray-coating a resin varnish on a carrier film or metal foil with a spray apparatus, this is dried. A resin sheet can be produced by these methods.

Although the said coating apparatus is not specifically limited, For example, a roll coater, a bar coater, a knife coater, a gravure coater, a die coater, a comma coater, a curtain coater, etc. can be used. Among these, a method using a die coater, a knife coater, and a comma coater is preferable. Thereby, the resin sheet which does not have a void and has the thickness of a uniform insulating layer can be manufactured efficiently.

It is preferable to select a film that is easy to handle because an insulating layer is formed on the film. Moreover, since the carrier film is peeled after laminating the insulating layer of the resin sheet on the inner layer circuit board surface, it is preferable that the resin sheet is easily peeled after being laminated on the inner layer circuit board. Accordingly, it is preferable to use, for example, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, or a thermoplastic resin film having heat resistance such as a fluorine resin or a polyimide resin. Among these carrier films, a film made of polyester is most preferable. This facilitates peeling from the insulating layer with an appropriate strength.

It is preferable to select a film that is easy to handle because an insulating layer is formed on the carrier film. Moreover, since the film is peeled after the insulating layer of the resin sheet is laminated on the inner layer circuit board surface, it is preferable that the resin sheet is easily peeled after being laminated on the inner layer circuit board. Therefore, it is preferable to use, for example, a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a thermoplastic resin film having heat resistance such as a fluorine resin, or a polyimide resin. Among these films, a film composed of polyester is most preferable. This facilitates peeling from the insulating layer with an appropriate strength.

Although the thickness of the said film is not specifically limited, 1-100 micrometers is preferable and 3-50 micrometers is especially preferable. When the thickness of the film is within the above range, handling is easy and the flatness of the surface of the insulating layer is excellent.

Similar to the film, the metal foil may be used after being peeled off after laminating a resin sheet on the inner circuit board, or may be used by etching the metal foil as a conductor circuit. The metal foil is not particularly limited. For example, copper and / or copper-based alloy, aluminum and / or aluminum-based alloy, iron and / or iron-based alloy, silver and / or silver-based alloy, gold and gold-based alloy, Metal foils such as zinc and zinc alloys, nickel and nickel alloys, tin and tin alloys can be used.

The thickness of the metal foil is not particularly limited, but is preferably 0.1 μm or more and 70 μm or less. Further, it is preferably 1 μm or more and 35 μm or less, more preferably 1.5 μm or more and 18 μm or less. If the thickness of the metal foil is less than the above lower limit, the metal foil is scratched, pinholes are generated, and when the metal foil is etched and used as a conductor circuit, plating variations, circuit disconnection, etching during circuit pattern molding There is a risk of infiltration of chemicals such as liquid and desmear liquid. When the upper limit is exceeded, the thickness variation of the metal foil increases or the surface roughness variation of the metal foil roughened surface increases. There is a case.

The metal foil may be an ultrathin metal foil with a carrier foil. The ultrathin metal foil with a carrier foil is a metal foil obtained by laminating a peelable carrier foil and an ultrathin metal foil. Since an ultra-thin metal foil layer can be formed on both sides of the insulating layer by using an ultra-thin metal foil with a carrier foil, for example, when forming a circuit by a semi-additive method, etc. By electroplating the metal foil directly as the power feeding layer, the ultrathin copper foil can be flash etched after the circuit is formed. By using an ultra-thin metal foil with a carrier foil, even with an ultra-thin metal foil having a thickness of 10 μm or less, for example, a reduction in handling properties of the ultra-thin metal foil in a pressing process, and cracking or cutting of the ultra-thin copper foil are prevented. Can do. The thickness of the ultrathin metal foil is preferably 0.1 μm or more and 10 μm or less. Furthermore, it is preferably 0.5 μm or more and 5 μm or less, more preferably 1 μm or more and 3 μm or less. When the thickness of the ultrathin metal foil is less than the lower limit, the ultrathin metal foil is damaged after peeling the carrier foil, the pinhole of the ultrathin metal foil is generated, and the circuit pattern is formed by the generation of the pinhole. Plating variation, disconnection of circuit wiring, penetration of chemicals such as etching liquid and desmear liquid, etc. may occur. If the above upper limit is exceeded, the thickness variation of the ultrathin metal foil will increase or the ultrathin metal foil There may be a case where the roughness of the roughened surface becomes large.
Usually, an ultrathin metal foil with a carrier foil peels off the carrier foil before forming a circuit pattern on the press-molded laminate.

Next, a laminated board is demonstrated.

The laminate of the present invention is formed by molding at least one prepreg described above. Thereby, the laminated board which has the outstanding heat resistance and adhesiveness, and was further excellent in the electrical property can be obtained.

In the case of a single prepreg, a metal foil or film is stacked on both upper and lower surfaces or one surface.
Two or more prepregs can be laminated. When two or more prepregs are laminated, a metal foil or film is laminated on the outermost upper and lower surfaces or one surface of the laminated prepreg. In addition, what is used for the said resin sheet can be used for the metal foil or film used for a laminated board.

Next, a laminate can be obtained by heating and pressurizing a laminate of a prepreg and a metal foil and / or a film.
The heating temperature is not particularly limited, but is preferably 150 to 240 ° C, and particularly preferably 180 to 220 ° C.
Moreover, the pressure to pressurize is not particularly limited, but is preferably 2 to 5 MPa, and particularly preferably 2.5 to 4 MPa.

Next, the printed wiring board will be described. Since there are various methods for producing a printed wiring board, an example will be described below, but it is not particularly limited.

Using a laminated board having copper foil on both sides, forming through holes with a drill or the like, filling the through holes by plating, and then applying a predetermined conductor circuit (inner layer circuit) on both sides of the laminated board by etching or the like An inner layer circuit board is produced by forming and roughening the conductor circuit such as blackening treatment.

When the cyanate resin composition of the present invention is used, fine through-holes can be formed with a high yield as compared with the conventional case, and the unevenness of the wall after the formation of the through-hole is very small. In particular, when the through hole is formed by laser processing, the unevenness of the wall after forming the through hole becomes very small.

Next, the above-described resin sheet or the above-described prepreg is formed on the upper surface and / or the lower surface of the inner layer circuit board, and is heated and pressed.
Specifically, the resin sheet or prepreg and the inner layer circuit board are combined and subjected to vacuum heating and pressing using a vacuum pressurizing laminator apparatus or the like. Thereafter, the insulating layer can be formed on the inner circuit board by heat-curing with a hot air drying device or the like.
Although it does not specifically limit as conditions to heat-press form here, if an example is given, it can implement at the temperature of 60-160 degreeC, and the pressure of 0.2-3 MPa. Moreover, it is although it does not specifically limit as conditions to heat-harden, If an example is given, it can implement in temperature 140-240 degreeC and time 30-120 minutes.

Alternatively, the insulating layer can also be formed on the inner layer circuit board by superimposing the resin sheet or prepreg on the inner layer circuit board and then heat-pressing the resin sheet or prepreg using a flat plate press apparatus or the like.
Although it does not specifically limit as conditions to heat-press form here, If an example is given, it can implement at the temperature of 140-240 degreeC, and the pressure of 1-4 MPa.

The laminated body obtained by the above-described method can form a new conductive wiring circuit by metal plating after roughening the surface of the insulating layer with an oxidizing agent such as permanganate or dichromate. it can.

When the cyanate resin composition of the present invention is used, it is excellent in fine wiring processing as compared with the prior art, and forms a wiring with a very narrow conductor width (line) and conductor (space) when a conductor circuit is formed with a high yield. be able to.

Thereafter, the insulating layer is cured by heating. Although the temperature to harden | cure is not specifically limited, For example, it can be hardened in the range of 160 to 240 degreeC. Preferably it is made to harden | cure at 180 to 200 degreeC.
Next, an opening is provided in the insulating layer by using a carbonic acid laser device, and an outer layer circuit is formed on the surface of the insulating layer by electrolytic copper plating to achieve conduction between the outer layer circuit and the inner layer circuit. The outer layer circuit is provided with a connection electrode portion for mounting a semiconductor element.
After that, a solder resist is formed on the outermost layer, the connection electrode part is exposed so that a semiconductor element can be mounted by exposure and development, nickel gold plating treatment is performed, and a printed wiring board is obtained by cutting to a predetermined size. it can.

When the cyanate resin composition of the present invention is used, since metal atoms such as nickel do not remain in the insulating layer as compared with the case of using a conventional epoxy resin composition during nickel gold plating, the electrical reliability is excellent.

Next, a semiconductor device will be described.

A semiconductor device can be manufactured by mounting a semiconductor element on the printed wiring board described above. The mounting method and the sealing method of the semiconductor element are not particularly limited. For example, a semiconductor element and a printed wiring board are aligned using a flip chip bonder or the like, and a connection electrode portion on the printed wiring board and a solder bump of the semiconductor element are aligned. Thereafter, the solder bump is heated to the melting point or higher by using an IR reflow device, a hot plate, or other heating device, and the connection electrode portion on the printed wiring board and the solder bump are connected by fusion bonding. And a semiconductor device can be obtained by filling and hardening a liquid sealing resin between a printed wiring board and a semiconductor element.

Hereinafter, although an example and a comparative example explain the present invention in detail, the present invention is not limited to this.

Example 1
1. Preparation of resin varnish 22.0% by weight of novolak cyanate resin (Lonza Japan Co., Ltd., Primaset PT-30), 13.0% by weight of cresol novolac epoxy resin (N-690, manufactured by Dainippon Ink & Chemicals, Inc.) Compound represented by formula (1) (1-phenyl-3- (4-tert-butylstyryl) -5- (4-tert-butylphenyl) pyrazoline) Chuo Gosei Co., Ltd., HR-50 0.05 parts by weight, Resin varnish is mixed with N, N-dimethylformamide so that the solid content is 70% by weight with spherical silica (average particle size 0.5 μm) 65.0% by weight, cobalt naphthenate 0.1% by weight as inorganic filler. Got.

2. Preparation of Prepreg The resin varnish prepared as described above was impregnated into a base material and dried at 150 ° C. for 5 minutes to obtain a 0.1 mm prepreg.

3. Fabrication of laminated plate A 12 μm thick copper foil (3EC-M3VLP made by Mitsui Metals) was superimposed on both sides of the prepreg produced as described above, and heat-press molded at 220 ° C. and 3 MPa, and a 0.1 mm copper foil was formed on both sides. The laminated board which has is obtained.
The thickness of the laminated board was 0.4 mm.

4). Fabrication of Printed Wiring Board The laminated board obtained above was subjected to through hole processing using a 0.1 mm drill bit, and then filled with through holes by plating. Further, a circuit was formed on both sides by etching and used as an inner layer circuit board. The prepreg obtained above was superposed on the front and back of the inner layer circuit board, and this was subjected to vacuum heating and press molding at a temperature of 100 ° C. and a pressure of 1 MPa using a vacuum pressurizing laminator apparatus. This was heated and cured at 170 ° C. for 60 minutes in a hot air drying apparatus to obtain a laminate.

Next, the surface electrolytic copper foil layer was subjected to blackening treatment, and a φ60 μm via hole for interlayer connection was formed by a carbon dioxide gas laser. Next, it is immersed in a swelling solution at 70 ° C. (Atotech Japan Co., Swelling Dip Securigant P) for 5 minutes, and further immersed in an aqueous solution of potassium permanganate at 80 ° C. (Concentrate Compact CP, manufactured by Atotech Japan) for 15 minutes. Then, it neutralized and the desmear process in a via hole was performed. Next, after the surface of the electrolytic copper foil layer is etched by about 1 μm by flash etching, electroless copper plating is performed with a thickness of 0.5 μm, a resist layer for electrolytic copper plating is formed with a thickness of 18 μm, and pattern copper plating is performed. The film was post-cured by heating at 60 ° C. for 60 minutes. Next, the plating resist was peeled off and the entire surface was flash etched to form a pattern of L / S = 20/20 μm.
Finally, a solder resist (PSR4000 / AUS308 manufactured by Taiyo Ink Co., Ltd.) having a thickness of 20 μm was formed on the circuit surface to obtain a printed wiring board.

5. Manufacturing of Semiconductor Device A printed wiring board used for manufacturing a semiconductor device is a printed wiring board obtained as described above, and provided with a connecting electrode portion subjected to nickel gold plating corresponding to a solder bump arrangement of a semiconductor element. The thing was cut into a size of 50 mm × 50 mm and used. A semiconductor element (TEG chip, size 15 mm × 15 mm, thickness 0.8 mm) has a solder bump formed of a eutectic of Sn / Pb composition, and a circuit protective film of the semiconductor element is a positive photosensitive resin (Sumitomo Bakelite). What was formed by company CRC-8300) was used. In assembling the semiconductor device, first, a flux material was uniformly applied to the solder bumps by a transfer method, and then mounted on a multilayer printed wiring board by thermocompression bonding using a flip chip bonder device. Next, after solder bumps were melt-bonded in an IR reflow furnace, a liquid sealing resin (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4152S) was filled and the liquid sealing resin was cured to obtain a semiconductor device. The curing condition of the liquid sealing resin was a temperature of 150 ° C. and 120 minutes.

(Example 2, Comparative Example 1, and Comparative Example 2)
Example 2, Comparative Example 1, and Comparative Example 2 were the same as in Example 1 except that the resin varnish was prepared according to the recipe shown in Table 1. Resin varnish, prepreg, laminate, resin sheet, printed wiring board A semiconductor device was manufactured.
The raw materials used are shown below.
(1) Cyanate resin / Novolac type cyanate resin: Lonza Japan Co., Ltd. “Primaset PT-30”, cyanate equivalent 124
(2) Epoxy resin / cresol novolac type epoxy resin: “N-690” manufactured by Dainippon Ink & Chemicals, Inc.), epoxy equivalent of 220 g / eq
(3) Maleimide resin / 3-ethyl-5-methyl-4-maleimidophenyl) methane: manufactured by Keisei Kasei Co., Ltd., “BMI-70”
(4) Compound represented by formula (1) / 1-phenyl-3- (4-tertiarybutylstyryl) -5- (4-tertiarybutylphenyl) pyrazoline: manufactured by Chuo Gosei Co., Ltd., “Product No. HR-50 "
(5) Full Hole Sein: “Part No. Fluorescein” manufactured by Kanto Chemical Co.
(6) Curing accelerator / Cobalt naphthenate: Nippon Kagaku Sangyo Co., Ltd. “Part No. Naphthenic Acid Co”
(7) Inorganic filler / fused silica; manufactured by Admatechs, “Part No. SO-25R”, average particle 0.5 μm

Example and comparative examples of resin varnishes, and resin varnishes prepared according to the formulation table, prepregs prepared using the resin varnishes, laminates, resin sheets, printed wiring boards, semiconductor devices, and other evaluation results Is shown in Table 1.

(Evaluation methods)
The evaluation was performed by the following method.

(1) Glass transition temperature The copper foil of the laminated board which has copper foil on the both surfaces obtained above is etched on the whole surface, a sample of a predetermined size is cut out, and 5 using a DMA apparatus (DMA 2980 manufactured by TA Instruments). While increasing the temperature at a rate of ° C./minute, a dynamic viscoelasticity was measured by applying a strain of a frequency of 1 Hz. The glass transition temperature was a temperature at which tan δ exhibited a maximum value.

(2) Solder heat resistance After the obtained laminated plate was cut into a 50 mm × 50 mm grinder saw, a sample in which only 1/4 of the copper foil was left by etching was prepared, and measured according to JISC 6481. In the measurement, after performing a PCT moisture absorption treatment at 121 ° C., 100% for 2 hours, it was immersed in a solder bath at 288 ° C. for 30 seconds, and then the presence or absence of appearance abnormality was examined.

(3) Light shielding properties The obtained laminate is etched on the entire surface to remove copper, and a solder resist (“PSR-4000” manufactured by Taiyo Ink) is applied to both sides of the substrate to a thickness of 50 μm at 80 ° C. Dried for 15 minutes.
Then, a negative film is applied to one surface, and 365 nm, 1.2 J / cm 2 of ultraviolet light is irradiated from the other surface with an ultraviolet irradiator (manufactured by Oak Manufacturing), developed with a sodium carbonate solution, and a negative film is applied. The presence of remaining solder resist on the surface was examined.
When the solder resist remains, light is transmitted to the solder resist on the surface to which the negative film is applied, indicating that at least a part of the solder resist is cured. In Table 1, this was designated as “with back exposure”. On the other hand, when no solder resist remains, it can be determined that light is not transmitted. This was defined as “no back exposure” in Table 1.

As is clear from Table 1, Examples 1 and 2 are the results of using the cyanate resin composition of the present invention containing both the cyanate resin and the compound represented by the general formula (1) as essential components. The transition temperature was high, and solder heat resistance and UV shielding were excellent.

On the other hand, since Comparative Example 1 did not contain the compound represented by the general formula (1), back exposure occurred.
Moreover, since the comparative example 2 used fluorescein, the glass point transition temperature fell.

The cyanate resin composition of the present invention has high glass point transfer, excellent solder heat resistance, and does not cause back exposure even with double-sided simultaneous exposure, so it can be usefully used for interposers and semiconductor devices that are thin and require high performance. .

Claims (8)

A cyanate resin composition comprising a cyanate resin and a compound represented by the following formula (1) as essential components.

(Wherein R ¹ and R ² represent hydrogen or a substituent selected from the group consisting of a hydroxyl group, an ethyl group, a methyl group, a butyl group, a tertiary butyl group, a phenyl group, and a carboxyl group; ¹ and R ² may be the same or different from each other. A prepreg obtained by impregnating a base material with the cyanate resin composition according to claim 1.   A metal-clad laminate having a metal foil on at least one surface of a resin-impregnated substrate layer obtained by impregnating the cyanate resin composition according to claim 1 in a substrate.   A metal-clad laminate obtained by superimposing a metal foil on at least one surface of the prepreg according to claim 1 or a laminate obtained by superimposing two or more of the prepregs, and heating and pressing. The resin sheet formed by forming the resin layer which consists of a cyanate resin composition of Claim 1 on a film or metal foil.   A printed wiring board comprising the metal-clad laminate according to claim 3 for an inner circuit board. The printed wiring board according to claim 6, wherein at least one layer of the prepreg according to claim 2 is laminated on the inner layer circuit board. A semiconductor device in which a semiconductor element is mounted on the printed wiring board according to claim 6.