JP2011084711A - Resin composition for circuit board, prepreg, laminate, printed wiring board, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a circuit board, which has a low thermal expansion rate and excellent heat resistance and adhesiveness with a conductor circuit; a prepreg using the resin composition; a laminate; a printed wiring board; and a semiconductor device. <P>SOLUTION: The resin composition for a circuit board includes following compounds as essential constituents: a compound (A) having two or more maleimide groups in the molecule; a compound (B) having two or more amino groups in the molecule and having an aromatic ring structure; and a compound (C) wherein hydroxy groups are bonded individually to two or more adjacent carbon atoms constituting an aromatic ring. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition for circuit boards, 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.

  If the printed wiring board is made thinner, the mounting reliability will decrease and the warpage of the printed wiring board will increase. Therefore, the thermal expansion coefficient of the resin composition used for the printed wiring board will be lowered, and the glass transition temperature will be increased. Various methods have been studied.

  As a resin composition having both a low coefficient of thermal expansion and a high glass transition temperature, it is generally known to react a maleimide resin and a diamine compound (for example, described in Patent Documents 1 and 2). In order to fully develop low thermal expansion coefficient and high heat resistance, it is necessary to completely react maleimide resin and diamine compound, but it is necessary to react at high temperature in order to completely react. Since the reaction does not proceed sufficiently in the reaction at a low temperature, a sufficient low coefficient of thermal expansion and high heat resistance could not be obtained. Further, when reacted at a high temperature, the maleimide resin self-polymerizes, so that the curing shrinkage increases, and when used for a printed wiring board or the like, sufficient adhesion with a conductor circuit cannot be obtained.

JP 05-86138 A JP 2006-104337 A

  The present invention provides a resin composition for a circuit board having a low coefficient of thermal expansion, excellent heat resistance and adhesion to a conductor circuit, and a prepreg, a laminate, a printed wiring board, and a semiconductor device using the same. To do.

Such an object is achieved by the present invention described in the following items [1] to [8].
[1] (A) a compound having two or more maleimide groups in the molecule, (B) a compound having two or more amino groups in the molecule and having an aromatic ring structure, and (C) an aromatic ring A resin composition for a circuit board, comprising as an essential component a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms that constitute the above.
[2] The compound (C) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting the aromatic ring is at least one selected from the group consisting of dihydroxynaphthalene, catechol, and pyrogallol [1] [3] The resin composition for circuit boards according to [3], wherein the compound (B) having two or more amino groups in the molecule and having an aromatic ring structure is diaminodiphenylsulfone [1] or [ [2] A prepreg obtained by impregnating a substrate with the circuit board resin composition according to any one of [1] to [3].
[5] A laminate having a metal foil on at least one side of a laminate obtained by superposing at least one prepreg according to the item [4].
[6] A resin sheet obtained by forming an insulating layer made of the resin composition for circuit boards according to any one of [1] to [3] on a film or a metal foil.
[7] A printed wiring board produced using at least one selected from the group consisting of the prepreg according to the item [4], the laminate according to the item [5], and the resin sheet according to the item [6]. .
[8] A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to the item [7].

  The resin composition for a circuit of the present invention has a low coefficient of thermal expansion, excellent heat resistance, and excellent adhesion to a conductor circuit when used for a printed wiring board or the like.

  Hereinafter, the resin composition for circuit boards, the prepreg, the laminated board, the printed wiring board, and the semiconductor device of the present invention will be described.

The resin composition for circuit boards of the present invention can be impregnated in a base material such as a glass fiber base material and used for a prepreg and a laminate using the prepreg.
Moreover, since the resin composition for circuit boards 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 resin composition for a circuit 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 motherboard.

  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 resin composition for circuit boards of the present invention will be described.

The resin composition for circuit boards of the present invention comprises (A) a compound having two or more maleimide groups in the molecule, (B) two or more amino groups in the molecule, and an aromatic ring structure. An essential component is a compound and (C) a compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring. As a result, a low coefficient of thermal expansion can be achieved, and the heat resistance and the adhesion to the conductor circuit are excellent.

The compound (A) having two or more maleimide groups in the molecule (hereinafter sometimes referred to as “(A) maleimide resin”) has a maleimide group having a five-membered planar structure. Since the double bond of the group is easy to interact between molecules and is more polar, it exhibits strong intermolecular interaction with maleimide groups, benzene rings, and other compounds having a planar structure, and suppresses molecular motion. Therefore, the coefficient of thermal expansion of the cured product of the circuit resin composition can be reduced, and the heat resistance is excellent.

  The (A) maleimide resin is not particularly limited. For example, 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2 ′-[4- (4-maleimidophenoxy) Phenyl] propane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 4-methyl-1,3-phenylenebismaleimide, N, N′-ethylenedimaleimide, N, N′-hexamethylene Examples thereof include bismaleimides such as dimaleimide and polymaleimides such as polyphenylmethane maleimide. Considering a low water absorption rate, 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane and bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane are particularly preferable.

  The (A) maleimide resin may be used alone or in combination of two or more.

  The content of the (A) maleimide resin is not particularly limited, but is 60 to 95% by weight in the resin composition excluding silica, aluminum hydroxide, and other inorganic fillers in the entire circuit resin composition. Is preferred. More preferably, it is 70 to 85% by weight. Thereby, the resin composition for circuits can express a low linear expansion coefficient effectively. (A) When content of maleimide resin is less than the said lower limit, a linear expansion coefficient may not become low enough, mounting reliability may fall, or the curvature of a printed wiring board may become large. When the upper limit is exceeded, the peel strength may be lowered with respect to the adhesion between the conductor circuit and the resin layer.

  The compound (B) having two or more amino groups in the molecule and having an aromatic ring structure (hereinafter sometimes referred to as (B) aromatic diamine compound) reacts with (A) maleimide resin. By making it, the thermal expansion coefficient of the hardened | cured material of the resin composition for circuits can further be reduced, and heat resistance further improves.

  Furthermore, since the (B) aromatic diamine compound has nitrogen atoms in the molecule, the cured product obtained by reacting with the (A) maleimide resin has high adhesion to the conductor circuit.

(B) The aromatic diamine compound is not particularly limited as long as it is a compound having two or more amino groups in the molecule and one or more aromatic ring structures. For example, m-phenylenediamine, Aromatic diamine compounds having one aromatic ring such as p-phenylenediamine, o-xylenediamine, biphenyl diamine compounds, diphenyl ether diamine compounds, benzophenone diamine compounds, diphenylsulfone diamine compounds, diphenylmethane diamine compounds, diphenyl Three aromatic rings such as propane-based diamine compounds, diphenylthioether diamine compounds, etc., aromatic diamine compounds having two aromatic rings, bis (phenoxy) benzene-based diamine compounds, bis (phenoxyphenyl) sulfone-based diamine compounds, etc. Have Aromatic diamine compounds having four aromatic rings such as aromatic diamine compounds, bis (phenoxy) diphenylsulfone diamine compounds, bis (phenoxyphenyl) hexafluoropropane diamine compounds, bis (phenoxyphenyl) propane diamine compounds, and the like. Which can be used alone or as a mixture.
Among these, aromatic diamine compounds having 2 or more and 4 or less aromatic rings are preferable.
Such compounds include, for example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone having two aromatic rings, , 3′-diaminodiphenylsulfone, 1,5-diaminonaphthalene, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane, 3,3′-diethyl-4,4′-diamino Diphenylmethane, 4,4 ′-(p-phenylenediisopropylidene) dianiline having 3 aromatic rings, 3,1,4-bis (4-aminophenoxy) benzene, 2,2 having 3 aromatic rings -Bis [4- (4-aminophenoxy) phenyl] propane and the like.
Moreover, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, etc. are preferable from the viewpoint of making the resin composition have a low coefficient of thermal expansion.

Although the compounding quantity of (B) aromatic diamine compound is not specifically limited, 0.8-1.2 are preferable as for the equivalent ratio of (A) maleimide resin and (B) aromatic diamine compound. When the equivalent ratio is less than 0.8 or exceeds 1.2, an unreacted compound may remain and heat resistance may decrease.

  (C) A compound in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter sometimes referred to as “compound (C)”) includes (A) maleimide resin and (B) The reaction of the aromatic diamine compound can be promoted.

The compound (C) easily leaves the hydrogen ion of its structure.
The hydrogen ion released from the compound (C) is added to the C—C double bond of the maleimide group of the (A) maleimide resin, and one carbon of the double bond becomes a cation.
As a result, the nitrogen atom of the (B) aromatic diamine compound is likely to nucleophilic attack the CC double bond of the (A) maleimide resin, and it is assumed that the curing reaction can be promoted.
Therefore, in the presence of the compound (C), the (A) maleimide resin and the (B) aromatic diamine compound can react even at a low temperature. It is assumed that the coefficient of thermal expansion can be further reduced and the heat resistance is further improved.

  In addition, the compound (C) suppresses the self-polymerization of the (A) maleimide resin and does not cause distortion in the cross-linked structure of the cured resin composition, so it is presumed that the residual stress is small and the adhesiveness to the conductor circuit is excellent. .

The compound (C) may have a substituent other than a hydroxyl group. As the compound (C), a monocyclic compound represented by the following general formula (1) or a polycyclic compound represented by the following general formula (2) can be used. You may use together.

(In the above general formula (1), one of R ₁ and R ₅ is a hydroxyl group, and when one is a hydroxyl group, the other is hydrogen, a hydroxyl group, or a substituent other than a hydroxyl group. R ₂ , R ₃ , R ₄ are hydrogen. , Hydroxyl groups or substituents other than hydroxyl groups.)

(In the general formula (2), one of R ₁ and R ₇ is a hydroxyl group, and when one is a hydroxyl group, the other is hydrogen, a hydroxyl group or a substituent other than a hydroxyl group. R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, a hydroxyl group or a substituent other than a hydroxyl group.)

Specific examples of the monocyclic compound represented by the general formula (1) include, for example, catechol, chlorocatechol, methoxycatechol, methylcatechol, methylcatechol, butylcatechol, 3,5-di-t-butylcatechol pyrogallol, Examples thereof include gallic acid, gallic acid ester, and derivatives thereof. From the viewpoint of reaction promotion, pyrogallol is preferred.

Specific examples of the polycyclic compound represented by the general formula (2) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Of these, 1,2-dihydroxynaphthalene and 2,3-dihydroxynaphthalene are preferable from the viewpoint of ease of control of curability and the melting point and volatility.

The cured product of the circuit board resin composition means a state in which the reaction of the functional group of the curable resin component in the curable resin composition constituting the circuit board resin composition is substantially completed, For example, it can be evaluated by measuring the calorific value with a differential scanning calorimetry (DSC) device.
Specifically, this indicates a state in which this calorific value is hardly detected.
As a condition for obtaining a cured product of such a resin material, for example, it is preferably treated at 120 to 220 ° C. for 30 to 180 minutes, and particularly preferably treated at 180 to 230 ° C. for 45 to 120 minutes.

The resin composition for circuit boards of the present invention contains, as essential components, a compound containing two or more maleimide groups in the molecule, an aromatic diamine, and an aromatic compound having two or more hydroxyl groups at the ortho position. However, other resins, curing agents, curing accelerators, flame retardants, coupling agents, inorganic fillers, and other components may be added without departing from the object of the present invention.

Next, the prepreg will be described.

The prepreg of the present invention is obtained by impregnating a base material with the above-described resin composition for circuit boards. Thereby, the prepreg excellent in various characteristics, such as heat resistance, can be obtained.
Examples of the base material used in the prepreg of the present invention include glass fiber base materials such as glass fiber cloth and glass non-woven cloth, inorganic fiber base materials such as fiber cloth and non-fiber cloth containing inorganic compounds other than glass, and aromatic polyamide resins. And organic fiber base materials composed of organic fibers such as polyamide resin, aromatic polyester resin, polyester resin, polyimide resin, and fluororesin. 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 circuit board resin composition include, for example, using a solvent to make the circuit board resin composition into a resin varnish, immersing the base material in the resin varnish, and applying with various coaters. For example, a spraying method may be used. 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 resin composition for circuit boards, 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-methylpyrrolidone and the like.
Although the solid content in the resin varnish is not particularly limited, the solid content of the resin composition for circuit boards 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 resin composition for a circuit board and drying at a predetermined temperature, for example, 80 to 200 ° C.

Next, the resin sheet will be described.
A resin sheet using the circuit board resin composition is obtained by forming an insulating layer made of the resin varnish on a carrier film or a metal foil.

Although content of the resin composition for circuit boards 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 carrier film or a 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.

Since the carrier film forms an insulating layer on the carrier film, it is preferable to select one that is easy to handle. 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. Therefore, it is preferable to use a thermoplastic resin film having heat resistance such as a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a fluorine-based resin, or a polyimide resin, for example. Among these carrier films, a film made of polyester is most preferable. This facilitates peeling from the insulating layer with an appropriate strength.

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

Similar to the carrier film, the metal foil may be used after peeling a resin sheet on an inner circuit board and may be used after peeling 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 whose dielectric constant and dielectric loss tangent are low can be obtained.

In the case of a single prepreg, a metal foil or a carrier 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 carrier 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 carrier 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, although a printed wiring board is demonstrated, the manufacturing method of a printed wiring board is not specifically limited. For example, it can be manufactured as follows.

A laminated board having copper foil on both sides obtained above is prepared, a through hole is formed by a drill or the like, and after filling the through hole by plating, a predetermined conductor circuit ( The inner layer circuit board is manufactured by forming the inner layer circuit) and subjecting the conductor circuit to a roughening process such as a blackening process.

When the resin composition for a circuit 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 forming the through-hole is very small as compared with the conventional case.

Next, the above-described resin sheet or the above-described prepreg is formed on the upper and lower surfaces 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 resin composition for a circuit of the present invention is used, it is excellent in fine wiring processing compared to the prior art, and a conductor width (line) when a conductor circuit is formed and a wiring with a very narrow space between conductors (space) can be formed with high yield. can do.

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 / development, nickel gold plating treatment is performed, and it is cut into a predetermined size to obtain a multilayer printed wiring board. Can do.

When the circuit resin composition of the present invention is used, compared to the case where a conventional epoxy resin composition is used during nickel gold plating, no metal atoms such as nickel remain in the insulating layer, so that the electrical reliability is excellent.

Next, a semiconductor device will be described.
A semiconductor device can be manufactured by mounting a semiconductor element on a printed wiring board manufactured by the method 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 used, and the connection electrode part on the multilayer printed wiring board and the solder bump of the semiconductor element are aligned using a flip chip bonder or the like. 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 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.

When the resin composition for a circuit of the present invention is used, the printed wiring board can be prevented from warping even at a temperature of about 260 ° C. where the semiconductor element is mounted, and the mountability is excellent.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

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

Example 1
(1) Preparation of resin varnish 81.0 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 17.6 parts by weight of 3,3′-diaminodiphenylsulfone, 2,3- N-methylpyrrolidone was added to 1.4 parts by weight of dihydroxynaphthalene and 150 parts by weight of aluminum hydroxide (Showa Denko HP-360) to adjust the nonvolatile content to 65% to obtain a resin varnish.

(2) Manufacture of prepreg Using the above-mentioned resin varnish, 100 parts by weight of glass fiber cloth (thickness 0.18 mm, manufactured by Nitto Boseki Co., Ltd.) was impregnated with 80 parts by weight of resin varnish in a solid content, and 190 ° C. The prepreg having a resin content of 44.4% by weight was prepared by drying in a drying oven for 7 minutes.

(3) Manufacture of resin sheet Copper foil (Mitsui Metal Mining Co., Ltd., manufactured by bonding the resin varnish obtained above with a peelable carrier foil layer and an electrolytic copper foil layer having a thickness of 0.5 to 5.0 μm. Apply to the electrolytic copper foil layer of micro thin Ex-3, carrier foil layer: copper foil (18 μm), electrolytic copper foil layer (3 μm) using a comma coater so that the resin layer after drying is 40 μm. This was dried for 10 minutes with a drying apparatus at 150 ° C. to produce a resin sheet.

(3) Manufacture of laminated board Two prepregs are stacked, and an electrolytic copper foil with a thickness of 18 μm (YGP-18 manufactured by Nihon Electrolytic Co., Ltd.) is stacked on top and bottom, followed by heat and pressure molding at a pressure of 4 MPa and a temperature of 220 ° C. for 180 minutes. A laminate having copper foil on both sides with a thickness of 0.4 mm was obtained.

(4) Production 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) Manufacture of semiconductor device The printed wiring board is a printed wiring board obtained as described above, and is provided with a connection electrode portion subjected to nickel gold plating corresponding to the solder bump arrangement of the semiconductor element. It cut | disconnected and used for the magnitude | size of * 50mm. 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)
78.2 parts by weight of 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane, 20.4 parts by weight of 3,3'-diaminodiphenylsulfone, and 1.4 parts by weight of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 3)
83.9 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 14.6 parts by weight of 3,3′-diaminodiphenylsulfone, and 1.5 by weight of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 4)
76.7 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 32.5 parts by weight of 3,3′-diaminodiphenylsulfone, and 1.7 parts by weight of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 5)
82.0 parts by weight of 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane, 17.6 parts by weight of 3,3'-diaminodiphenylsulfone, and 1.4 parts by weight of 1,2-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 6)
82.5 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 17.7 parts by weight of 3,3′-diaminodiphenylsulfone, 0.8 parts by weight of pyrogallol, aluminum hydroxide A resin varnish was prepared in the same manner as in Example 1 except that the amount was changed to 150 parts by weight, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 7)
81.0 parts by weight of 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane, 17.6 parts by weight of 4,4'-diaminodiphenylsulfone, and 1.4 parts by weight of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Example 8)
83.8 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 14.7 parts by weight of 4,4′-diaminodiphenylmethane, and 1.5 parts by weight of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

Example 9
75.8 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 22.9 parts by weight of 4,4 ′-(p-phenylenediisopropylidene) dianiline, 2,3-dihydroxy A resin varnish was prepared in the same manner as in Example 1 except that 1.3 parts by weight of naphthalene and 150 parts by weight of aluminum hydroxide were used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained. It was.

(Example 10)
79.1 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 4,4′-diamino-3,3′-diethyl-5,5′-dimethyldiphenylmethane (manufactured by Ihara Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 except that 19.5 parts by weight of product name: Cure Hard MED), 1.4 parts by weight of 2,3-dihydroxynaphthalene, and 150 parts by weight of aluminum hydroxide were used. Thus, a prepreg, a resin sheet, a laminated board, a printed wiring board, and a semiconductor device were obtained.

(Example 11)
80.6 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 3,3′-diethyl-4,4′-diaminodiphenylmethane (trade name: Kayahard A-, manufactured by Nippon Kayaku Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 except that A) was 17.9 parts by weight, 2,3-dihydroxynaphthalene was 1.5 parts by weight, and aluminum hydroxide was 150 parts by weight. Sheets, laminates, printed wiring boards, and semiconductor devices were obtained.

(Example 12)
78.9 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 19.8 parts by weight of 1,4-bis (4-aminophenoxy) benzene, and 2,3-dihydroxynaphthalene Except that 1.3 parts by weight and 150 parts by weight of aluminum hydroxide were used, a resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

(Example 13)
72.6 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (trade name BAPP manufactured by Wakayama Seika) A resin varnish was prepared in the same manner as in Example 1, except that 26.1 parts by weight, 1.3 parts by weight of 2,3-dihydroxynaphthalene, and 150 parts by weight of aluminum hydroxide were prepared, and a prepreg, a resin sheet, A laminated board, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 1)
Except for 84.1 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 15.9 parts by weight of 4,4′-diaminodiphenylmethane, and 150 parts by weight of aluminum hydroxide, A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

(Comparative Example 2)
75.3 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 24.7 parts by weight of 4,4 ′-(p-phenylenediisopropylidene) dianiline, 150 aluminum hydroxide A resin varnish was prepared in the same manner as in Example 1 except for changing to parts by weight, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 3)
72.0 parts by weight of bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 28.0 parts by weight of 4,4 ′-(p-phenylenediisopropylidene) dianiline, and 150% of aluminum hydroxide A resin varnish was prepared in the same manner as in Example 1 except for changing to parts by weight, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 4)
Except for 81.0 parts by weight of 2,2 ′-[4- (4-maleimidophenoxy) phenyl] propane, 19.0 parts by weight of 3,3′-diaminodiphenylsulfone, and 150 parts by weight of aluminum hydroxide. A resin varnish was prepared in the same manner as in Example 1 to obtain a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device.

(Comparative Example 5)
81.0 parts by weight of 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane, 17.6 parts by weight of 3,3'-diaminodiphenylsulfone, and 1.4 parts by weight of 1,6-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 6)
81.0 parts by weight of 2,2 '-[4- (4-maleimidophenoxy) phenyl] propane, 17.6 parts by weight of 3,3'-diaminodiphenylsulfone, and 1.4 parts by weight of 2,7-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

(Comparative Example 7)
76.7 parts by weight of a cresol novolac type epoxy resin (Epiclon N-690 manufactured by DIC, epoxy equivalent 220), 32.5 parts by weight of 3,3′-diaminodiphenylsulfone, and 1.7 weights of 2,3-dihydroxynaphthalene A resin varnish was prepared in the same manner as in Example 1 except that 150 parts by weight of aluminum hydroxide was used, and a prepreg, a resin sheet, a laminate, a printed wiring board, and a semiconductor device were obtained.

The following evaluation was performed about the resin varnish and laminated board which were obtained by each Example and the comparative example. Each evaluation is shown below together with the evaluation method. The obtained results are shown in Table 1.

Evaluation method (1) Gel time In accordance with JIS C6521, an amount of resin varnish with a solid mass of 0.15 g is placed on a cure plate heated to 170 ° C., and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.

(2) Glass transition temperature The entire surface of the double-sided copper clad laminate having a thickness of 0.4 mm obtained in the examples and comparative examples was etched.
6 mm × 25 mm test pieces were prepared, and the temperature was raised at 5 ° C./min using a DMA apparatus (dynamic viscoelasticity measuring apparatus DMA983 manufactured by TA Instruments), and the peak position of tan δ was determined as the glass transition temperature. It was.

(3) Linear expansion coefficient The copper foil of the laminated board which has a copper foil on both surfaces of 0.4 mm thickness obtained by the said Example and the comparative example was etched on the whole surface, and the test of 5 mm x 20 mm from the obtained laminated board A piece was prepared, and the linear expansion coefficient in the plane direction (X direction) was measured under the condition of 5 ° C./min by using a TMA apparatus (manufactured by TA Instruments).

(4) Peel strength A 100 mm x 20 mm test piece was prepared from a laminate having copper foil on both sides of 0.4 mm thickness obtained in the above examples and comparative examples, and the peel strength at 23 ° C was measured.
The peel strength measurement was performed according to JIS C 6481.

(5) Reaction rate The reaction rate was calculated | required by measuring using a DSC apparatus (The differential scanning calorimetry DSC2920 by TA Instruments company).
It calculated | required by following Formula (I) by comparing the area of the exothermic peak by DSC reaction about both the unreacted resin composition and the resin composition after hardening. In addition, the measurement was performed in a nitrogen atmosphere at a heating rate of 10 ° C./min.
Reaction rate (%) = (1−area of reaction peak of resin composition after curing / reaction peak area of unreacted resin composition) × 100 (I)
Here, the exothermic peak of the unreacted resin composition was obtained by impregnating a base material with a resin varnish comprising the resin compositions of Examples and Comparative Examples of the present invention, air drying at 40 ° C. for 10 minutes, 40 ° C. and 1 kPa. This is an exothermic peak obtained when DSC measurement was performed using a sample from which the solvent was removed in vacuum for 1 hour.
The heat generation peak of the resin composition after curing was obtained by etching the copper foil of the laminate having copper foil on both sides of the examples of the present invention and the comparative example having a thickness of 0.4 mm, and removing the resin from the surface as a sample. As an exothermic peak when DSC measurement is performed.

As is apparent from the table, Examples 1 to 13 contain a compound containing two or more maleimide groups in the molecule, an aromatic diamine compound, and an aromatic compound having two or more hydroxyl groups at the ortho position. It was a laminate using the circuit board resin composition of the present invention, had a high glass transition temperature, a low coefficient of thermal expansion, and excellent adhesion.
Furthermore, since the gel time was short, it was excellent in productivity.
On the other hand, Comparative Examples 1 to 6 had a long gel time and deteriorated productivity.

In all of Comparative Examples 1 to 4, sufficient values were not obtained in the peel strength measurement showing adhesion.
Further, Comparative Examples 1 to 6 had a long gel time and were inferior in productivity.
It can be seen that it is necessary to cure at a higher temperature in order to obtain productivity equivalent to that of the example.
Moreover, from Comparative Example 3 to 7, it was found from the results of the reaction rate that the reaction rate was not sufficient and molding was not possible under the pressing conditions at 220 ° C. for 180 minutes.

Comparative Example 7 using an epoxy resin had a problem that the gel time was good, but the linear expansion coefficient was high.

All the printed wiring boards and semiconductor devices obtained in the examples were able to be manufactured with good yield. On the other hand, in all the comparative examples, the yield was poor, and in particular, the connection reliability between the semiconductor element and the printed wiring board at the time of manufacturing the semiconductor device was poor.

  The resin composition for circuit boards, the prepreg, and the laminate of the present invention have a high glass transition temperature, a low coefficient of thermal expansion, and excellent heat resistance. Thereby, it can be usefully used for a thin system-in-package substrate and semiconductor device.

Claims (8)

(A) a compound having two or more maleimide groups in the molecule, (B) a compound having two or more amino groups in the molecule and having an aromatic ring structure, and (C) constituting an aromatic ring A resin composition for circuit boards, comprising as an essential component a compound in which a hydroxyl group is bonded to two or more adjacent carbon atoms.   The compound (C) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting the aromatic ring is at least one selected from the group consisting of dihydroxynaphthalene, catechol, and pyrogallol. Resin composition for circuit board The resin composition for a circuit board according to claim 1 or 2, wherein the compound (B) having two or more amino groups in the molecule and having an aromatic ring structure is diaminodiphenyl sulfone. A prepreg obtained by impregnating a base material with the circuit board resin composition according to claim 1. A laminate having a metal foil on at least one surface of a laminate in which at least one prepreg according to claim 4 is laminated. The resin sheet formed by forming the insulating layer which consists of a resin composition for circuit boards in any one of Claim 1 thru | or on a film or metal foil. A printed wiring board produced using at least one selected from the group consisting of the prepreg according to claim 4, the laminate according to claim 5, and the resin sheet according to claim 6. A semiconductor device comprising a semiconductor element mounted on the printed wiring board according to claim 7.