KR20160118962A - Prepreg, resin substrate, metal clad laminated board, printed wiring board and semiconductor device - Google Patents

Abstract

According to the present invention, a prepreg material is prepared by impregnating a thermosetting resin composition in a fiber substrate. When a thermomechanical analysis and measurement operation is conducted on a cured product which is obtained by heating the prepreg material at 230C for two hours, a ratio (2/1) of 2, which is an average linear expansion coefficient calculated in the range of 150C to 250C in the in-plane direction of the cured product, and 1, which is an average linear expansion coefficient calculated in the range of 50C to 150C in the in-plane direction of the cured product, is in the range of 0.7 to 2.20. The average linear expansion coefficient 2 is equal to or less than 8.0 ppm/C.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a prepreg, a resin substrate, a metal-clad laminate, a printed wiring board,

The present invention relates to a prepreg, a resin substrate, a metal-clad laminate, a printed wiring board, and a semiconductor device.

2. Description of the Related Art In recent years, high density integration and high-density mounting of electronic components have been progressed in accordance with the demand for high-performance of electronic devices. In addition, due to high-density integration of electronic components and high-density mounting, miniaturization of semiconductor devices used in these electronic devices is rapidly proceeding. A printed circuit board used in a semiconductor device is required to have a high-density and fine circuit.

As a method of forming a fine circuit, a SAP (semi-additive process) method has been proposed. In the SAP method, first, the surface of the insulating layer is subjected to a roughening treatment to form an electroless metal plating film serving as a ground (base) on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper thickening of the circuit forming portion is performed by electrolytic plating. Next, the plating resist is removed, and then an electroless metal plating film other than the circuit forming portion is removed by flush etching to form a circuit on the insulating layer. According to the SAP method, since the metal layer to be laminated on the insulating layer can be made thinner, a finer circuit wiring becomes possible.

The semiconductor device is formed, for example, by mounting a semiconductor element on a printed wiring board. As a technique related to such a printed wiring board, for example, there is a technique described in Patent Document 1 below. Patent Document 1 discloses a printed wiring board using a thermosetting resin composition having a dihydrobenzoxazine ring and a thermosetting resin composition containing a thermosetting resin having a maleimide ring as an essential component. The thermosetting resin composition is characterized in that the content of the thermosetting resin having a maleimide ring is 3 to 30% by weight based on the total amount of the thermosetting resin having a dihydrobenzoxazine ring and the thermosetting resin having a maleimide ring.

Patent Document 1: JP-A-10-259248

A semiconductor device formed by mounting a semiconductor element on a printed wiring board is required to have excellent insulation reliability between wirings. Such a demand has become remarkable in recent years due to the increase in the wiring density of the printed wiring board. However, according to the study by the present inventors, it has been found that it is difficult to sufficiently obtain the insulation reliability of a printed wiring board under high temperature and high humidity in the technique described in Patent Document 1.

According to the present invention,

A prepreg obtained by impregnating a fiber substrate with a thermosetting resin composition,

The cured product obtained by subjecting the prepreg to heat treatment at 230 占 폚 for 2 hours is subjected to thermomechanical analysis to measure the average coefficient of linear expansion? ₁ in the in-plane direction of the cured product in the range of 50 占 폚 to 150 占 폚 Wherein a ratio (α ₂ / α ₁ ) of an average linear expansion coefficient α ₂ calculated in the range of 150 ° C. to 250 ° C. is 0.7 or more and 2.0 or less and the average linear expansion coefficient α ₂ is 8.0 ppm / Is provided.

According to the present invention, there is also provided a resin substrate including a cured product of the prepreg.

According to the present invention, there is also provided a metal-clad laminate provided with a metal foil on one side or both sides of a cured product of the prepreg, or on one side or both sides of a cured product of a laminate obtained by superposing two or more prepregs.

Further, according to the present invention, there is provided a printed wiring board obtained by circuit processing the resin substrate or the metal clad laminate, and a printed wiring board provided with one or more circuit layers.

According to the present invention, there is also provided a semiconductor device in which a semiconductor element is mounted on the circuit layer of a printed wiring board.

According to the present invention, it is possible to provide a prepreg, a resin substrate, and a metal-clad laminate capable of realizing a printed wiring board having fine circuit dimensions and excellent insulation reliability under high temperature and high humidity. Further, it is possible to provide a printed wiring board and a semiconductor device excellent in insulation reliability under high temperature and high humidity.

1 is a cross-sectional view showing an example of a structure of a metal-clad laminate according to the present embodiment.
2 is a cross-sectional view showing an example of the configuration of a printed wiring board in the present embodiment.
3 is a cross-sectional view showing an example of the configuration of a printed wiring board in the present embodiment.
4 is a cross-sectional view showing an example of the configuration of the semiconductor device in the present embodiment.
5 is a cross-sectional view showing an example of the configuration of the semiconductor device in the present embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same constituent elements are denoted by the same reference numerals, and a description thereof will be omitted. Also, the drawing is a schematic view and does not coincide with the actual dimensional ratio. Further, "~" between the numbers in the sentence indicates the following in the above unless otherwise specified.

First, the prepreg in this embodiment will be described.

The prepreg is used to form an insulating layer of a printed wiring board. The prepreg is a sheet-like material obtained, for example, by impregnating a fiber substrate with a thermosetting resin composition (P) (hereinafter also referred to as a resin composition (P)) in the present embodiment and then semi-curing .

The resin substrate is used for forming an insulating layer of the printed wiring board.

Here, the resin substrate contains a cured product of the prepreg. Such a resin substrate can be obtained, for example, by thermally curing a single prepreg. The resin substrate can also be obtained by heat-curing a laminate obtained by laminating two or more prepregs. As the resin substrate, a layer composed of an insulating material other than the fiber base material and the resin composition (P) constituting the prepreg may be provided on one surface or both surfaces of the prepreg. Examples of such a layer include a hard coat layer for improving the scratch resistance of a resin substrate. The resin substrate having the hard coat layer can be obtained, for example, by bringing the hard coat layer into close contact with the one side or both sides of the cured product of the prepreg through the primer layer. Alternatively, the resin substrate can be obtained by heating the prepreg before and after hardening in a state in which the hard coat layer is in close contact with one side or both sides of the prepreg, thereby curing the prepreg and fusing the prepreg and the hard coat layer.

The prepreg can be used, for example, to form an insulating layer in the buildup layer or an insulating layer in the core layer in the printed wiring board.

When the prepreg is used for forming the insulating layer in the core layer of the printed wiring board, for example, two or more prepregs may be stacked and the obtained stacked body may be heat-cured to form an insulating layer for the core layer .

From the standpoint of the insulation reliability under high temperature and high humidity of the printed wiring board and the reliability of connection between the semiconductor element and the printed wiring board, the prepreg satisfies the following conditions. That is, when thermomechanical analysis is performed on a cured product obtained by heating the prepreg at 230 占 폚 for 2 hours (hereinafter simply referred to as "cured product"), (Α ₂ / α ₁ ) of the average linear expansion coefficient α ₂ calculated in the range of 150 ° C. to 250 ° C. with respect to the average linear expansion coefficient α ₁ calculated in the range is not less than 0.7 and not more than 2.0. It is preferable that? ₂ /? ₁ is 0.75 or more and 1.5 or less, more preferably 0.8 or more and 1.2 or less.

The cured product of the prepreg described above can be obtained by simply heating the prepreg at a predetermined temperature (230 DEG C), but a cured product obtained by heating under a pressurized condition is preferable. This is because, in the cured product formed by heating and pressing the prepreg, the physical properties thereof are more stable, and accurate physical property evaluation becomes possible. When a prepreg is heated and pressed to form a cured product, the cured product can be obtained, for example, by heating under pressure at 4 MPa and 230 DEG C for 2 hours.

The resin substrate made of only the cured prepreg of the prepreg satisfies the same conditions as the above-mentioned cured prepreg. When the resin substrate has a layer other than the cured product of the prepreg, only the cured product of the prepreg may satisfy the above conditions. In the following description, the condition of the cured product of the prepreg is a condition in which the cured product of the prepreg of the resin substrate must be satisfied.

In the present embodiment, the average coefficient of linear expansion? ₁ and? ₂ are determined by using a TMA (thermomechanical analysis) apparatus (Q400, manufactured by TA Instrument) at a temperature range of 30 ° C. to 260 ° C., / min, a load of 10 g, and a linear expansion coefficient (CTE) in the plane direction (XY direction) measured under the compression mode.

In the case of the cured product, when a value of? ₂ /? ₁ satisfies the above-described range, a change in the stress caused by the difference in coefficient of linear expansion between the circuit layer and the insulating layer Can be reduced. This makes it possible to maintain the adhesion between the circuit layer and the insulating layer even when the obtained printed wiring board or semiconductor device is placed for a long period of time under a severe temperature change. From the above, it is considered that the use of such a prepreg can improve the insulation reliability of the obtained printed wiring board under high temperature and high humidity.

In the case of a cured product, when the value of? ₂ /? ₁ satisfies the above-described range, even if a large change occurs in the environmental temperature of the resulting semiconductor device, the stress caused by the difference in linear expansion coefficient between the printed wiring board and the semiconductor element The change can be reduced. As a result, displacement of the semiconductor element relative to the printed wiring board can be further suppressed, and connection reliability and temperature cycle reliability at high temperatures between the semiconductor element and the printed wiring board can be further improved.

From the viewpoint of further improving the reliability of insulation of the printed wiring board under high temperature and high humidity and the reliability of connection between the semiconductor element and the printed wiring board, the prepreg further satisfies the following conditions. That is, when thermomechanical analysis is performed on the cured product, the average coefficient of linear expansion? ₂ in the in-plane direction of the cured product in the range of 150 to 250 占 폚 is 8.0 ppm / 占 폚 or less. The average coefficient of linear expansion? ₂ is preferably 7.5 ppm / ° C or less, and particularly preferably 7.2 ppm / ° C or less. The lower limit value is not particularly limited, but may be 0.1 ppm / DEG C or higher, for example.

When the average linear expansion coefficient? ₂ of the cured product satisfies the above-described range, the stress generated due to the difference in linear expansion coefficient between the circuit layer and the insulating layer when the resulting printed wiring board is exposed to a high temperature such as a solder reflow Can be reduced. This makes it possible to maintain the adhesion between the circuit layer and the insulating layer even when the obtained printed wiring board or semiconductor device is placed for a long period of time under a severe temperature change. This makes it possible to further improve the insulation reliability of the obtained printed wiring board under high temperature and high humidity.

When the average coefficient of linear expansion? ₂ of the cured product satisfies the above-described range, it is caused by the difference in linear expansion coefficient between the printed wiring board and the semiconductor element when the obtained semiconductor device is exposed to a high temperature such as a solder reflow Stress can be reduced. As a result, displacement of the semiconductor element relative to the printed wiring board can be further suppressed, and connection reliability and temperature cycle reliability at high temperatures between the semiconductor element and the printed wiring board can be further improved.

From the viewpoint of improving the insulation reliability of the printed wiring board under high temperature and high humidity and improving the reliability of connection between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the following conditions. That is, when thermomechanical analysis is performed on the cured product, the average coefficient of linear expansion? ₁ calculated in the in-plane direction of the cured product in the range of 50 ° C to 150 ° C is preferably 7.5 ppm / / ° C or less, and particularly preferably 6.5 ppm / ° C or less. The lower limit value is not particularly limited, but may be 0.1 ppm / DEG C or higher, for example.

In the cured product, if the average coefficient of linear expansion? ₁ satisfies the above range, the stress caused by the difference in coefficient of linear expansion between the circuit layer and the insulating layer is reduced even if a great change occurs in the environmental temperature of the obtained printed wiring board . This makes it possible to maintain the adhesion between the circuit layer and the insulating layer even when the obtained printed wiring board or semiconductor device is placed for a long period of time under a severe temperature change. This makes it possible to further improve the insulation reliability of the obtained printed wiring board under high temperature and high humidity.

When the average linear expansion coefficient? ₁ of the cured product satisfies the above-described range, the resulting semiconductor device exhibits a stress caused by the difference in coefficient of linear expansion between the printed wiring board and the semiconductor element when exposed to a high temperature. Can be reduced. As a result, displacement of the semiconductor element relative to the printed wiring board can be further suppressed, and connection reliability and temperature cycle reliability at high temperatures between the semiconductor element and the printed wiring board can be further improved.

In order to achieve the average coefficient of linear expansion? ₁ ,? ₂ ,? ₂ /? ₁ , the kind of the constituent components of the resin composition (P) of the prepreg, the blending amount of each component, the prepreg manufacturing method, It is important. Specific examples of the constituent components of the resin composition (P) include a maleimide compound (A), a benzoxazine compound (B), an inorganic filler (C), an epoxy resin (D) E), fiber substrate, curing accelerator, and the like.

From the viewpoint of further enhancing the connection reliability between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the following conditions. That is, when a cured product was subjected to a thermomechanical analysis measurement using a thermomechanical analyzer, a process of raising the temperature from 30 DEG C to 260 DEG C at a rate of 10 DEG C / min and a process of maintaining the temperature at 260 DEG C for one hour, The reference length L ₀ in the longitudinal direction of the cured product before the thermomechanical analysis measurement, and the maximum thermal expansion amount from the reference length L ₀ of the cured product as L ₁ , When the thermal expansion amount from the length L ₀ is L ₂ , the dimensional shrinkage ratio represented by 100 × (L ₁ -L ₂ ) / L ₀ is preferably 0.15% or less, more preferably 0.10% or less. The lower limit value is not particularly limited, but may be 0.00% or more, for example.

The longitudinal direction of the cured product indicates the conveying direction of the prepreg (so-called MD).

Generally, when the semiconductor device is exposed to a high temperature, the stress accumulated in the insulating layer in the printed wiring board (for example, the stress accumulated in the fibrous substrate when the prepreg is heated and cured) is released, do. Further, when the resin is cooled from high temperature to room temperature, the resin component of the insulating layer tends to shrink. On the other hand, in the case of the cured product, when the dimensional shrinkage rate satisfies the above-described range, the resulting semiconductor device can reduce the stress caused by shrinkage of the insulating layer in the printed wiring board when exposed to a high temperature. This makes it possible to maintain the adhesion between the insulating layer and the circuit layer even when the semiconductor device is placed for a long period of time in a state of severe temperature change. As a result, it is possible to further improve the insulation reliability of the obtained printed wiring board under high temperature and high humidity. Further, positional deviation of the semiconductor element from the printed wiring board can be further suppressed, and the connection reliability and the temperature cycle reliability at a high temperature between the semiconductor element and the printed wiring board can be further improved.

In order to achieve such a dimensional shrinkage ratio, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D) E), fiber substrate, curing accelerator, etc., and the prepreg preparation method, etc., are suitably controlled.

The cured product is subjected to a process of raising the temperature from 30 ° C to 300 ° C at a rate of 10 ° C / min using a thermomechanical analyzer, and a process of decreasing the temperature of the cured product from 300 ° C to 30 ° C at a rate of 10 ° C / The longitudinal length of the cured product before the thermomechanical analysis measurement is set as the reference length L ₀ and the length in the longitudinal direction of the cured product at 30 캜 in the temperature lowering process is defined as L ₁ , the dimensional change rate represented by 100 x (L ₁ -L ₀ ) / L ₀ is preferably -0.20% or more, and more preferably -0.15% or more. The lower limit value is not particularly limited, but may be 0.00% or less, for example.

The longitudinal direction of the cured product indicates the conveying direction of the prepreg (so-called MD).

In the cured product, when the dimensional change rate satisfies the above range, the stress caused by the dimensional change of the insulating layer in the printed wiring board can be reduced when the resulting semiconductor device is exposed to a severe temperature change. This makes it possible to maintain the adhesion between the insulating layer and the circuit layer even when the semiconductor device is placed for a long period of time in a state of severe temperature change. As a result, it is possible to further improve the insulation reliability of the obtained printed wiring board under high temperature and high humidity. Further, positional deviation of the semiconductor element from the printed wiring board can be further suppressed, and the connection reliability and the temperature cycle reliability at a high temperature between the semiconductor element and the printed wiring board can be further improved.

In order to achieve such a dimensional change rate, it is preferable to use the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D) E), fiber substrate, curing accelerator, etc., and the prepreg preparation method, etc., are suitably controlled.

From the viewpoint of improving the rigidity and heat resistance of the obtained printed wiring board, the prepreg preferably satisfies the following conditions. That is, the cured product preferably has a glass transition temperature of 260 ° C or higher, more preferably 270 ° C or higher, and more preferably 280 ° C or higher, when the dynamic viscoelasticity measurement is performed on the cured product at a temperature raising rate of 5 ° C / Deg.] C or higher. As for the upper limit, for example, 400 占 폚 or lower is preferable. The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA).

When the glass transition temperature of the cured product obtained by the dynamic viscoelasticity measurement satisfies the above range, the rigidity of the printed wiring board obtained becomes high, and warping of the printed wiring board at the time of mounting can be further reduced. As a result, in the obtained semiconductor device, the displacement of the semiconductor element relative to the printed wiring board can be further suppressed, and the connection reliability between the semiconductor element and the printed wiring board can be further improved.

In order to achieve such a glass transition temperature, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D) It is important to suitably control the type and amount of the binder (E), the fiber substrate, the curing accelerator and the like, and the prepreg manufacturing method.

From the viewpoint of further improving the balance of the rigidity, heat resistance and stress relaxation ability of the printed wiring board obtained by using the prepreg, the prepreg preferably satisfies the following conditions. That is, with respect to the cured product, when performing the dynamic viscoelasticity measurement, the storage modulus E 'at ₃₀ of the cured 30 ℃ water, and preferably not less than 10GPa, more preferably not less than 20GPa. The upper limit value is not particularly limited, but may be, for example, 40 GPa or less.

When 30 ℃ cured product storage elastic modulus E _'30 in the satisfaction of the range, the performance balance of the rigidity and heat resistance, the stress relaxation ability of the printed wiring board obtained is improved, it can be more reduced than that of the printed circuit board at the time of mounting the warp have. This makes it possible to further suppress the positional deviation of the semiconductor element from the printed wiring board with respect to the obtained semiconductor device. As a result, the connection reliability between the semiconductor element and the printed wiring board can be further improved.

From the viewpoint of further improving the balance of the rigidity, heat resistance and stress relaxation ability of the printed wiring board obtained by using the prepreg, the prepreg preferably satisfies the following conditions. That is, when with respect to the cured product, performing the dynamic viscoelasticity measurement, the "storage elastic modulus E at 30 ℃ about _{250 '30} ratio (E' ₃₀ / E _'250) of the storage elastic modulus E of the curing 250 ℃ water, More preferably 1.05 or more and 1.75 or less.

In the cured product, when E _'30 / E' ₂₅₀ satisfies the above range, the change in the modulus of elasticity of the printed wiring board with respect to the temperature change can be further suppressed. Thus, even if a large temperature change occurs, the insulating layer is hardly deformed, and the positional deviation of the semiconductor element with respect to the printed wiring board can be suppressed. As a result, the connection reliability between the semiconductor element and the printed wiring board can be further improved.

Such a storage modulus E _'30 and E' ₃₀ / E 'in order to achieve _250, the components of the resin composition (P), maleimide compounds (A), benzoxazine compound (B), inorganic filler (C) , Epoxy resin (D), low stress material (E), fiber substrate, curing accelerator, etc., prepreg preparation method and the like.

From the standpoint of further enhancing the fine wiring workability of the prepreg cured product or the resin substrate, the prepreg preferably satisfies the following conditions. That is, when the mass of the cured product after drying at 120 ° C for 1 hour is defined as the first mass and the mass of the cured product after drying at 120 ° C for 1 hour is regarded as the second mass after the cured product is treated under the following conditions, (The first mass) - (the second mass)} / (the sum of the areas of the front and back surfaces of the cured product)] x 100 is preferably 1.2 g / m ² or less.

<Condition>

The cured product was immersed in a 3 g / L sodium hydroxide solution (solvent: diethylene glycol monobutylether 11.1 vol%, ethylene glycol 3.6 vol%, pure water 85.3 vol%) at 60 DEG C for 5 minutes to swell the cured product . Subsequently, the swollen cured product is dipped in a harmony treatment aqueous solution (60 g / L of sodium permanganate and 45 g / L of sodium hydroxide) at 80 DEG C for 5 minutes to coarsen the cured product. Subsequently, the cured product subjected to the coarsened treatment is immersed in a neutralized solution (5.0% by volume of 98% by mass of sulfuric acid, 0.8% by volume of sulfuric acid hydroxylamine and 94.2% by volume of pure water) at 40 DEG C for 5 minutes to neutralize the cured product.

If the amount of the film of the cured product satisfies the above range, the cured product of the prepreg or the fine wiring workability of the resin substrate can be improved. This is presumably because the cured product or the resin substrate of the prepreg having the amount of the thin film defined by the above formula is not more than the upper limit value can maintain the adhesion to the metal layer (circuit layer) even if the surface is roughened.

In order to attain such a thin film amount, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material E), fiber substrate, curing accelerator, etc., and the prepreg preparation method, etc., are suitably controlled.

The thickness of the prepreg is, for example, 20 μm or more and 220 μm or less. When the thickness of the prepreg is within the above range, the balance between the mechanical strength and the productivity is particularly excellent, and a resin substrate suitable for a thin printed wiring board can be obtained.

1 is a cross-sectional view showing an example of a structure of a metal-clad laminate 200 according to the present embodiment. As shown in Fig. 1, the metal clad laminate 200 is provided with metal foils 105 on both sides of an insulating layer 301 composed of a hardened prepreg. The metal-clad laminate 200 can be used to form an insulating layer of a printed wiring board. Although the metal foil 105 is provided on both sides of the insulating layer 301 in the embodiment shown in Fig. 1, the metal foil 105 is formed on one side of the insulating layer 301 . The insulating layer 301 may be composed of a multilayer body obtained by superposing a plurality of prepregs (two or more pieces).

It is also preferable that the metal-clad laminate 200 satisfy the following conditions from the viewpoint of further improving the insulation reliability under high temperature and high humidity of the obtained printed wiring board. That is, it is preferable that the rate of change in peel strength when the metal-clad laminate 200 is stored in an environment of 135 ° C and 85% RH for 100 hours is 30% or less. Here, the rate of change in peel strength is expressed by 100 x (P ₁ -P ₂ ) / P ₁ . P ₁ is the peel strength between the cured product of the prepreg before storage (the insulating layer 301 and the metal foil 105) measured according to JIS C-6481: 1996, and P ₂ is the peel strength of the prepreg after storage And the peel strength between the cured product (the insulating layer 301 and the metal foil 105).

In the metal-clad laminate 200, if the rate of change in peel strength satisfies the above range, the insulation reliability under high temperature and high humidity of the printed wiring board obtained can be improved. This is presumably because the metal-clad laminate 200 having the rate of change in peel strength as defined by the above formula can maintain the adhesion to the metal layer (circuit layer) even if it is exposed for a long time under high temperature and high humidity.

In order to achieve such a rate of change in the peel strength, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), the epoxy resin (D) It is important to appropriately control the kind and amount of the binder (E), the fiber substrate, the curing accelerator, etc., the prepreg manufacturing method, and the method of manufacturing the metal clad laminate 200, respectively.

Next, a method of manufacturing the prepreg will be described.

The prepreg is, for example, a sheet-like material obtained by impregnating a fiber substrate with the resin composition (P) in the present embodiment, and then semi-curing. The sheet-like material having such a structure is excellent in various characteristics such as dielectric properties, mechanical and electrical connection reliability under high temperature and high humidity, and is suitable for manufacturing an insulating layer of a printed wiring board.

The method of impregnating the resin composition (P) with the fiber substrate is not particularly limited, and examples thereof include a method of dissolving the resin composition (P) in a solvent to prepare a resin varnish and immersing the fiber substrate in the resin varnish, A method in which the resin varnish is sprayed onto the fiber substrate by spraying, a method in which the resin substrate (P) composed of the resin composition (P) And a method of laminating them.

Next, a method of manufacturing the metal-clad laminate 200 using the prepreg obtained as described above will be described. A method of manufacturing the metal-clad laminate 200 using the prepreg is as follows, for example.

First, the metal foil 105 is superimposed on the upper and lower surfaces or one side of the outer side of the laminate in which two or more prepregs or prepregs are superimposed. Next, they are bonded under a high vacuum condition using a laminator device or a becquerel device. Alternatively, the metal foil 105 may be simply superimposed on the upper and lower surfaces or one side of the outer side of the laminate in which two or more prepregs or prepregs are stacked without using the laminator device or the bakrete device.

Subsequently, the laminate of the prepreg (or a laminate of two or more prepregs) and the metal foil 105 is heated and pressed to obtain the metal laminate plate 200. Here, it is preferable to continue the pressurization at the time of heat press forming until the end of cooling.

The heating temperature at the time of the heat press molding is preferably 120 占 폚 or higher and 250 占 폚 or lower, more preferably 150 占 폚 or higher and 240 占 폚 or lower.

The pressure at the time of the hot pressing is preferably from 0.5 MPa to 5 MPa, and more preferably from 2.5 MPa to 5 MPa.

After the heat press molding, if necessary, post-curing may be performed with a thermostat or the like. The post-curing temperature is preferably 150 占 폚 to 300 占 폚, and more preferably 250 占 폚 to 300 占 폚.

In addition, a printed wiring board can be obtained by using the metal-clad laminate 200 or the resin substrate as a core substrate.

Hereinafter, the prepreg, the metal-clad laminate 200 and the respective materials used in the production of the resin substrate will be described in detail.

Examples of the metal constituting the metal foil 105 include metals such as copper, copper alloys, aluminum, aluminum alloys, silver, silver alloys, gold and gold alloys, zinc, zinc alloys, nickel, Fe-Ni alloys such as tin-based alloys, iron, iron-based alloys, Koba (trademark), 42 alloys, Invar, Super Invar, W, Mo and the like. Among them, copper or a copper alloy is preferable as the metal constituting the metal foil 105 because of its excellent conductivity, easy circuit formation by etching, and low cost. That is, the metal foil 105 is preferably a copper foil.

As the metal foil 105, a carrier metal foil or the like may also be used.

The thickness of the metal foil 105 is preferably 0.5 μm or more and 20 μm or less, more preferably 1.5 μm or more and 18 μm or less.

Next, the fiber substrate used in the present embodiment will be described.

The fiber base material is not particularly limited, and examples thereof include glass fiber base materials such as glass woven fabric and glass nonwoven fabric; Polyamide resin fibers such as polyamide resin fibers, aromatic polyamide resin fibers and wholly aromatic polyamide resin fibers; Polyester-based resin fibers such as polyester resin fibers, aromatic polyester resin fibers and wholly aromatic polyester resin fibers; A synthetic fiber substrate composed of a woven or non-woven fabric comprising a polyimide resin fiber or a fluororesin fiber as a main component; Paper base materials mainly composed of kraft paper, cotton linters, or mixed paper of linter and kraft pulp; And the like. Any one of them may be used. Of these, glass fiber substrates are preferred. This makes it possible to obtain a resin substrate having low water absorption, high strength and low thermal expansion.

The thickness of the fiber base material is not particularly limited, but is preferably 5 占 퐉 or more and 150 占 퐉 or less, more preferably 10 占 퐉 to 100 占 퐉, and more preferably 12 占 퐉 to 90 占 퐉. By using the fiber base material having such a thickness, the handling property at the time of producing the prepreg can be further improved.

When the thickness of the fiber substrate is not more than the upper limit, the impregnability of the resin composition (P) in the fiber substrate is improved, and generation of strand voids and deterioration of insulation reliability can be suppressed. In addition, it is possible to facilitate the formation of the through holes for the resin substrate and the insulating layer 301 by laser such as carbon dioxide, UV, excimer and the like. When the thickness of the fibrous base material is not lower than the above lower limit value, the strength of the fibrous base material and the prepreg can be improved. As a result, the handling property is improved, the preparation of the prepreg is facilitated, and the warpage of the resin substrate can be suppressed.

Examples of the glass fiber substrate include glass fibers formed by one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass The substrate is suitably used.

The resin composition (P) is a thermosetting resin composition used for forming an insulating layer in a printed wiring board and includes a maleimide compound (A), a benzoxazine compound (B), and an inorganic filler (C) .

As the maleimide compound (A), it is preferable to include the maleimide compound (A1) represented by the following formula (1).

[Chemical Formula 1]

(1), n ₁ is an integer of 0 or more and 10 or less, X ₁ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (1a), a group represented by the formula: -SO ₂ - A group represented by "-CO- &quot;, an oxygen atom or a single bond, R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, a is independently an integer of 0 to 4, b are each independently an integer of 0 or more and 3 or less)

(2)

(In the formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 to 30 carbon atoms and n ₂ is an integer of 0 or more)

The alkylene group of 1 to 10 in X ₁ is not particularly limited, but a linear or branched alkylene group is preferable.

Specific examples of the straight chain alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylenerene group, a trimethylene group, A pentamethylene group, and a hexamethylene group.

The alkylene group of the branched chain, _{specifically, -C (CH 3) 2 -} ( iso-propylene _{group), -CH (CH 3) -} , -CH (CH 2 CH 3) -, -C (CH 3 An alkylmethylene group such as - (CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -C (CH ₂ CH ₃ ) ₂ -CH ₂ -, and the like.

The number of carbon atoms of the alkylene group in X ₁ may be 1 or more and 10 or less, but is preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less. Specifically, examples of the alkylene group having such a carbon number include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

Each R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, but is preferably a hydrocarbon group having 1 or 2 carbon atoms, concretely, for example, a methyl group or an ethyl group.

Also, a is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, more preferably 0. B is an integer of 0 or more and 3 or less, preferably 0 or 1, and more preferably 0.

N ₁ is an integer of from 0 to 10, preferably from 0 to 6, more preferably from 0 to 4, particularly preferably from 0 to 3. It is more preferable that the maleimide compound (A) contains at least one compound of the formula (1) in which n ₁ is 1 or more. As a result, the insulating layer obtained from the resin composition (P) exhibits better heat resistance.

In the formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 to 30 carbon atoms and n ₂ is an integer of 0 or more.

The hydrocarbon group having 6 or more and 30 or less carbon atoms and having an aromatic ring may be a hydrocarbon group comprising only an aromatic ring or may have a hydrocarbon group other than an aromatic ring. Y may be an aromatic ring or two or more aromatic rings, and when two or more aromatic rings are present, these aromatic rings may be the same or different. The aromatic ring may be either a monocyclic structure or a polycyclic structure.

Specific examples of the hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms include benzene, biphenyl, naphthalene, anthracene, fluorene, phenanthrene, indacene, terphenyl, acenaphthylene, And a divalent group obtained by removing two hydrogen atoms from the nucleus of a compound having aromaticity.

These aromatic hydrocarbon groups may have a substituent. Here, the aromatic hydrocarbon group having a substituent means that a part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted with a substituent. As the substituent, for example, an alkyl group can be mentioned.

The alkyl group as this substituent is preferably a linear alkyl group. The number of carbon atoms is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 4 or less. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl and sec-butyl.

Such a group Y preferably has a group obtained by removing two hydrogen atoms from benzene or naphthalene and the group represented by the formula (1a) is preferably a group represented by any one of the following formulas (1a-1) and (1a- . As a result, the insulating layer obtained from the resin composition (P) exhibits better heat resistance.

(3)

In the formulas (1a-1) and (1a-2), R ₄ is independently a hydrocarbon group having 1 to 6 carbon atoms. e is independently an integer of 0 or more and 4 or less, more preferably 0. [

In the group represented by the formula (1a), n ₂ may be an integer of 0 or more, but is preferably an integer of 0 or more and 5 or less, more preferably an integer of 1 or more and 3 or less, particularly preferably 1 or 2 Do.

From the above, the maleimide compound (A1) represented by the formula (1) is a compound wherein X ₁ is a linear or branched alkylene group having 1 to 3 carbon atoms and R ₁ is a hydrocarbon group having 1 or 2 carbon atoms , a is an integer of 0 or more and 2 or less, b is 0 or 1, and n ₁ is an integer of 1 or more and 4 or less. Alternatively, X ₁ is a group represented by any one of the formulas (1a-1) and (1a-2), and preferably, e is 0. As a result, the insulating layer obtained from the resin composition (P) exerts excellent heat shrinkability and chemical resistance.

As a preferable specific example of the maleimide compound (A1) represented by the above formula (1), for example, a maleimide compound represented by the following formula (1-1) is particularly preferably used.

[Chemical Formula 4]

The maleimide compound (A) may contain a maleimide compound (A2) of a different kind from the maleimide compound (A1) represented by the formula (1).

Examples of such maleimide compounds (A2) include 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylene diamine bismaleimide, N, N'- Aliphatic bismaleimide compounds such as maleimide, N, N'-1,3-propylene bismaleimide and N, N'-1,4-tetramethylene bismaleimide; Imide-extended bismaleimide, and the like. Of these, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane and imide-extended bismaleimide are particularly preferred. The maleimide compound (A2) may be used alone or in combination of two or more.

Examples of the imide-extended bismaleimide include a bismaleimide compound represented by the following formula (a1), a bismaleimide compound represented by the following formula (a2), a bis (maleimide) compound represented by the following formula Maleimide compounds and the like. Specific examples of the bismaleimide compound represented by formula (a1) include BMI-1500 (manufactured by Designer Molecules Inc., molecular weight: 1500). Specific examples of the bismaleimide compound represented by formula (a2) include BMI-1700 (manufactured by Designer Molecules, molecular weight 1700), BMI-1400 (manufactured by Designer Molecules, molecular weight 1400) Specific examples of the bismaleimide compound represented by formula (a3) include BMI-3000 (manufactured by Designer Molecules, molecular weight: 3000).

[Chemical Formula 5]

In the formula (a1), n represents an integer of 1 or more and 10 or less.

[Chemical Formula 6]

In the formula (a2), n represents an integer of 1 or more and 10 or less.

(7)

In the formula (a3), n represents an integer of 1 or more and 10 or less.

The content of the maleimide compound (A) contained in the resin composition (P) is not particularly limited, but the content of the maleimide compound (A) in the resin composition (P) is preferably 1.0% by mass, Or more and 25.0 mass% or less, more preferably 2.0 mass% or more and 22.0 mass% or less, and still more preferably 5.0 mass% or more and 20.0 mass% or less. When the content of the maleimide compound (A) is within the above range, the balance between the cured product of the obtained prepreg and the low heat shrinkability and chemical resistance of the resin substrate can be further improved.

The content of the maleimide compound (A1) contained in the maleimide compound (A) is not particularly limited, but it is preferably 30.0% by mass or more, more preferably 30.0% by mass or more, based on 100% by mass of the maleimide compound (A) Is preferably 100.0 mass% or less, more preferably 50 mass% or more and 100.0 mass% or less. When the content of the maleimide compound (A1) is within the above range, the balance of the cured product of the resulting prepreg and the low heat shrinkability and chemical resistance of the resin substrate can be further improved.

The lower limit of the weight average molecular weight (Mw) of the maleimide compound (A1) is not particularly limited, but is preferably 400 or more, and particularly preferably 800 or more. When the Mw is equal to or smaller than the lower limit value, occurrence of tacking on the prepreg can be suppressed. The upper limit of Mw is not particularly limited, but is preferably 4000 or less, more preferably 2500 or less. When the Mw is not more than the upper limit value, the impregnation property with respect to the fiber substrate is improved at the time of manufacturing the resin substrate, and a more uniform resin substrate can be obtained. The Mw of the maleimide compound (A1) can be measured by, for example, GPC (gel permeation chromatography, standard material: in terms of polystyrene).

The benzoxazine compound (B) is a compound having a benzoxazine ring. Examples of the benzoxazine compound (B) include one or more compounds selected from the compounds represented by the following formula (2) and the compounds represented by the following formula (3).

[Chemical Formula 8]

(2), each X ₂ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula "-SO ₂ -", a group represented by "-CO-" An oxygen atom or a single bond, R ₂ is independently a hydrocarbon group having 1 to 6 carbon atoms, and c is independently an integer of 0 to 4)

[Chemical Formula 9]

(3), each X ₃ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula "-SO ₂ -", a group represented by "-CO-" An oxygen atom or a single bond, R ₃ is independently a hydrocarbon group having 1 to 6 carbon atoms, and d is independently an integer of 0 to 4)

Examples of X ₂ and X _{3 in} the formulas (2) and (3) include the same groups as those described for X ₁ in the formula (1). R ₂ and R _{3 in} the formulas (2) and (3) can be the same as those described for R ₁ in the formula (1), and the formulas (2) and The c and d in the formula (3) can be the same as those described for the formula (1).

The benzoxazine compound (B) is preferably a compound represented by the formula (2) among the compound represented by the formula (2) and the compound represented by the formula (3). As a result, the insulating layer obtained from the resin composition (P) exerts excellent heat shrinkability and chemical resistance.

The compound represented by the above formula (2) is a compound wherein X ₂ is a linear or branched alkylene group having 1 to 3 carbon atoms and R ₂ is a hydrocarbon group having 1 or 2, Or less. Alternatively, X ₂ is a group represented by any one of the formulas (1a-1) and (1a-2), and c is preferably 0. As a result, the insulating layer obtained from the resin composition (P) exerts excellent heat shrinkability and chemical resistance.

Specific examples of the benzoxazine compound (B) include, for example, a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), a compound represented by the following formula A compound represented by the following formula (3-1), a compound represented by the following formula (3-2), and a compound represented by the following formula (3-3) .

[Chemical formula 10]

(In the above formula (2-3), each R is independently a hydrocarbon group having 1 to 4 carbon atoms)

(11)

[Chemical Formula 12]

The content of the benzoxazine compound (B) contained in the resin composition (P) is not particularly limited. When the total solids content of the resin composition (P) is 100 mass% Or more and 25.0 mass% or less, and more preferably 2.0 mass% or more and 15.0 mass% or less. When the content of the benzoxazine compound (B) is within the above range, it is possible to further improve the cured product of the obtained prepreg and the low heat shrinkability and chemical resistance of the resin substrate.

The content of the maleimide compound (A) contained in the resin composition (P) is preferably 35 mass% or more and 80 mass% or less based on 100 mass% of the total amount of the maleimide compound (A) and the benzoxazine compound (B) . This makes it possible to further improve the heat resistance, the low heat shrinkability, and the chemical resistance of the obtained cured product of the prepreg and the resin substrate.

The resin composition (P) according to the present embodiment may further include an epoxy resin (D).

Examples of the epoxy resin (D) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 '- Bisphenol-type epoxy resin), bisphenol-type epoxy resin (4,4 '- (1,4-phenylene diisophoradiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin , 4'-cyclohexadiene bisphenol type epoxy resin), and other bisphenol type epoxy resins; Novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, tetra phenol group ethane type novolak type epoxy resin and condensed ring aromatic hydrocarbon structure novolak type epoxy resin; Biphenyl-type epoxy resins; Aralkyl type epoxy resins such as xylylen type epoxy resins and biphenyl aralkyl type epoxy resins; Naphthalene type epoxy resins such as naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalene diol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin and naphthalene aralkyl type epoxy resin; Anthracene type epoxy resin; Phenoxy type epoxy resin; Dicyclopentadiene type epoxy resin; Norbornene type epoxy resin; Adamantane type epoxy resin; Fluorene-type epoxy resins, and the like.

As the epoxy resin (D), one type of epoxy resin (D) may be used alone, or two or more types may be used together, or one type or two or more types thereof and these prepolymers may be used in combination.

Of the epoxy resins (D), from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board, there can be mentioned bisphenol type epoxy resins, novolak type epoxy resins, biphenyl type epoxy resins, aralkyl type epoxy resins, An epoxy resin, an anthracene epoxy resin, and a dicyclopentadiene epoxy resin, and is preferably an aralkyl type epoxy resin, a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure And naphthalene type epoxy resins are more preferable.

As the bisphenol A type epoxy resin, "Epikote 828EL" and "YL980" manufactured by Mitsubishi Chemical Corporation can be used. As the bisphenol F type epoxy resin, "jER806H " and" YL983U "available from Mitsubishi Chemical Corporation, and" EPICLON 830S " As the bifunctional naphthalene type epoxy resin, "HP4032 "," HP4032D ", and "HP4032SS" As the tetrafunctional naphthalene type epoxy resin, "HP4700" and "HP4710" manufactured by DIC Corporation can be used. As the naphthol-type epoxy resin, "ESN-475V" manufactured by Shinnittoshi Kagaku Co., Ltd., "NC7000L" manufactured by Nippon Kayaku Co., Ltd., and the like can be used. "NC3000", "NC3000H", "NC3000L", "NC3000S", "NC3000S-H" and "NC3100" manufactured by Nippon Kayaku Co., Ltd., "ESN- "ESN-480" As the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene epoxy resin, "YX8800" manufactured by Mitsubishi Kagaku Co., Ltd. and the like can be used. As the naphthylene ether type epoxy resin, "HP6000", "EXA-7310", "EXA-7311", "EXA-7311L" and "EXA7311-G3" manufactured by DIC can be used.

As the epoxy resin (D), one type of epoxy resin (D) may be used alone, or two or more types thereof may be used together, or one type or two or more types thereof may be used in combination with these prepolymers.

Among these epoxy resins (D), an aralkyl type epoxy resin is particularly preferable. As a result, the heat-resistant solder heat resistance and flame retardancy of the resin substrate can be further improved.

The lower limit of the weight average molecular weight (Mw) of the epoxy resin (D) is not particularly limited, but is preferably 300 or more, particularly preferably 800 or more. When Mw is not less than the above lower limit value, it is possible to suppress the occurrence of the picking property on the prepreg. The upper limit of Mw is not particularly limited, but is preferably 20,000 or less, and particularly preferably 15,000 or less. When the Mw is less than the upper limit value, the impregnation property with respect to the fibrous substrate is improved at the time of making the prepreg, so that a more uniform prepreg can be obtained. The Mw of the epoxy resin can be measured by GPC, for example.

The content of the epoxy resin (D) contained in the resin composition (P) may be suitably adjusted according to the purpose, and is not particularly limited. However, when the total amount of the components excluding the inorganic filler (C) in the resin composition (P) is 100 mass%, it is preferably 1 mass% or more and 50 mass% or less. When the content of the epoxy resin (D) is not lower than the above lower limit value, the handling property is improved and the prepreg can be easily formed. When the content of the epoxy resin (D) is not more than the upper limit value, the strength and flame retardancy of the resulting printed wiring board are improved, the coefficient of linear expansion of the printed wiring board is lowered, and the effect of reducing warpage is improved.

The resin composition (P) according to the present embodiment preferably contains an inorganic filler (C). As a result, the storage elastic modulus E 'of the cured product of the obtained prepreg and the resin substrate can be improved. In addition, the coefficient of linear expansion of the obtained insulating layer 301 can be reduced.

Examples of the inorganic filler (C) include silicates such as talc, calcined clay, unbaked clay, mica and glass; Oxides such as titanium oxide, alumina, boehmite, silica, and fused silica; Carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; Hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; Sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; Borates such as zinc borate, barium metaborate, aluminum borate, calcium borate and sodium borate; Nitrides such as aluminum nitride, boron nitride, silicon nitride, and carbon nitride; Strontium titanate, strontium titanate, and titanate salts such as barium titanate.

Among these, talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide and magnesium hydroxide are preferable, and silica is particularly preferable. As the inorganic filler (C), one type of the inorganic filler (C) may be used alone, or two or more types may be used in combination.

The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 0.01 탆 or more, and more preferably 0.05 탆 or more. When the average particle diameter of the inorganic filler (C) is not lower than the lower limit value described above, the viscosity of the varnish can be prevented from becoming excessively high, and the workability at the time of production of the prepreg can be improved. The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 5.0 占 퐉 or less, more preferably 2.0 占 퐉 or less, and even more preferably 1.0 占 퐉 or less. When the average particle diameter of the inorganic filler (C) is not more than the upper limit value, the phenomenon such as settling of the inorganic filler (C) in the varnish can be suppressed and a more uniform resin layer can be obtained. In addition, when the circuit dimension L / S (line and space) of the printed wiring board is less than 20/20 m, it is possible to suppress the influence on the insulation between the wirings. The average particle diameter of the inorganic filler (C) is, for example, by laser diffraction type particle size distribution analyzer (HORIBA Co., Ltd., LA-500), by measuring the particle size of the particle size distribution on the volume basis, the median diameter (D ₅₀ ) Can be made an average particle diameter.

The inorganic filler (C) is not particularly limited, but an inorganic filler having an average particle diameter of monodisperse may be used, or an inorganic filler having an average particle diameter of polydispersity may be used. The inorganic fillers having an average particle diameter of monodisperse and / or polydisperse may be used alone or in combination of two or more.

The inorganic filler (C) is preferably a silica particle, more preferably a silica particle having an average particle diameter of 5.0 m or less, more preferably a silica particle having an average particle diameter of 0.1 m or more and 4.0 m or less, Particles are particularly preferred. As a result, the filling property of the inorganic filler (C) with respect to the fiber substrate can be further improved.

The content of the inorganic filler (C) contained in the resin composition (P) is not particularly limited, but it is preferably 50.0% by mass or more, more preferably 50.0% by mass or more, based on 100% by mass of the total solid content of the resin composition (P) Preferably 85.0 mass% or less, and more preferably 60.0 mass% or more and 80.0 mass% or less. When the content of the inorganic filler (C) is within the above range, the obtained prepreg cured product and the resin substrate can be made to have lower thermal expansion and lower absorption.

The resin composition (P) preferably further comprises a low stress material (E). As a result, the stress of the cured product of the obtained prepreg and the resin substrate can be relaxed, and adhesion with other members such as a circuit layer can be further improved.

Examples of the low stress material (E) include (meth) acrylic block copolymers; Silicon compounds; Acrylonitrile / butadiene rubber modified with a carboxyl group, an amino group, a vinyl acrylate group or an epoxy group; Aliphatic epoxy resins; And rubber particles, and the like.

The (meth) acrylic block copolymer is a block copolymer containing a (meth) acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, (Meth) acrylic acid alkyl esters such as t-butyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, and stearyl methacrylate; (Meth) acrylic acid esters having an alicyclic structure such as cyclohexyl acrylate, cyclohexyl methacrylate and the like; (Meth) acrylic acid esters having an aromatic ring such as benzyl methacrylate; (Fluoro) alkyl esters of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; A carboxyl group-containing acrylic monomer having a carboxyl group in the molecule such as acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, Mono (meth) acrylic acid esters and other hydroxyl group-containing acrylic monomers having a hydroxyl group in the molecule; Acrylic monomers having an epoxy group in the molecule such as glycidyl methacrylate, methyl glycidyl methacrylate and 3,4-epoxycyclohexylmethyl methacrylate; Allyl group-containing acrylic monomers having an allyl group in the molecule such as allyl acrylate and allyl methacrylate; silyl-containing acrylic monomers having a hydrolyzable silyl group in the molecule such as? -methacryloyloxypropyltrimethoxysilane and? -methacryloyloxypropyltriethoxysilane; And ultraviolet absorptive acrylic monomers having a benzotriazole-based ultraviolet absorptive group such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole.

Further, monomers other than the acrylic monomer may be used as the monomer component in the (meth) acrylic block copolymer. Examples of the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and? -Methylstyrene, conjugated dienes such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutene. .

The (meth) acrylic block copolymer is not particularly limited, and examples thereof include a diblock copolymer composed of two polymer blocks, a triblock copolymer composed of three polymer blocks, a triblock copolymer composed of four or more polymer blocks And multi-block copolymers.

Among them, the (meth) acrylic block copolymer is preferably a polymer block (soft block) having a low glass transition temperature (Tg) and a polymer block (S) having a low glass transition temperature (Tg), from the viewpoint of improving heat resistance, light resistance, A block copolymer in which polymer blocks (H) having a higher Tg (hard block) are alternately arranged is preferable, more preferably a polymer block (S) is in the middle and a polymer block (H) Triblock copolymer is preferred.

As specific preferred examples of the (meth) acrylic block copolymer in the resin composition (P), for example, the polymer block (S) is a polymer composed mainly of butyl acrylate (BA) Polystyrene acrylate-block-polymethyl methacrylate terpolymer (PMMA-b-PBA-b), which is a polymer composed mainly of methyl methacrylate (MMA) -PMMA).

Examples of the (meth) acrylic block copolymer include trade names of "Nano Strength M52N", "Nano Strength M22N", "Nano Strength M51", "Nano Strength M52", "Nano Strength M53" , PMMA-b-PBA-b-PMMA), trade names "Nano Strength E21" and "Nano Strength E41" (Akeama Co., PSt (polystyrene) -b-PBA-b-PMMA).

Examples of the silicone compound include a silicone rubber, a silicone oil, a silicone powder, a silicone resin, a silicone epoxy resin, an amine-modified silicone resin, an epoxy group, and a three-dimensional crosslinked silicone resin containing a phenyl group.

The aliphatic epoxy resin is preferably an aliphatic epoxy resin having no cyclic structure in addition to the glycidyl group, and more preferably a bifunctional or higher aliphatic epoxy resin having two or more glycidyl groups. Such an aliphatic epoxy resin is excellent because an epoxy group is hardly oxidized and an increase in elastic modulus due to thermal history hardly occurs.

Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile-butadiene rubber particles, crosslinked styrene-butadiene rubber particles, acrylic rubber particles, silicone particles and the like.

The core-shell-type rubber particles are rubber particles having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is composed of a glassy polymer and the core layer of the inner layer is composed of rubbery polymer, A three-layer structure composed of the glassy polymer, the intermediate layer made of a rubbery polymer and the core layer made of a glassy polymer, and the like. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate and the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include stapyloids AC3832, AC3816N (trade name, manufactured by Kanto Kasei Kasei) and Metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of crosslinked acrylonitrile-butadiene rubber (NBR) particles include XER-91 (average particle diameter 0.5 mu m, manufactured by JSR Corporation).

Specific examples of the crosslinked styrene-butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include Metbrene W300A (average particle diameter 0.1 mu m) and W450A (average particle diameter 0.2 mu m) (manufactured by Mitsubishi Rayon Co., Ltd.).

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) and core parts made of silicone of two-dimensional crosslinking main body are three- And core shell structure particles coated with silicon as a main component. As silicone rubber fine particles, commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Trefil E-500 and Trefil E-600 Can be used.

The content of the low stress material (E) contained in the resin composition (P) is not particularly limited, but is preferably 0.1 mass% or less, more preferably 100 mass% Or more and 10.0 mass% or less, and more preferably 1.0 mass% or more and 8.0 mass% or less. When the content of the low stress material (E) is within the above range, the stress of the cured product of the obtained prepreg or the resin substrate can be further relaxed, and the adhesiveness with other members such as a circuit layer can be further improved.

In addition, if necessary, a curing accelerator and a coupling agent may be appropriately added to the resin composition (P).

The curing accelerator is not particularly limited, and examples thereof include a phosphine compound, a compound having a phosphonium salt, and an imidazole-based compound, and one or more of these may be used in combination. Of these, imidazole-based compounds are preferred. The imidazole-based compound can promote the polymerization reaction of the maleimide compound (A) and the benzoxazine compound (B) more certainly because it is a compound having a particularly excellent function as a catalyst.

The imidazole-based compound is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2- , 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, Methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1 -cyanoethyl-2-undecylimidazole Sol, 1-cyanoethyl-2-phenylimidazole, and the like, and one or more of these may be used in combination. Among them, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferable. By using these compounds, the reaction between the maleimide compound (A) and the benzoxazine compound (B) is further promoted, the molding processability is improved, and the heat resistance of the obtained cured product is improved.

Examples of the phosphine compounds include alkylphosphines such as ethylphosphine and propylphosphine, and primary phosphines such as phenylphosphine; Dialkylphosphines such as dimethylphosphine and diethylphosphine, secondary phosphines such as diphenylphosphine, methylphenylphosphine and ethylphenylphosphine; Triphenylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, trialkylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, triphenylphosphine, Benzylphosphine, tritolylphosphine, tri-p-styrylphosphine, tris (2,6-dimethoxyphenyl) phosphine, tri-4-methylphenylphosphine, And tert-phosphine such as tri-2-cyanoethylphosphine. Of these, tertiary phosphines are preferably used.

Examples of the compound having a phosphonium salt include compounds having a tetraphenylphosphonium salt and an alkyltriphenylphosphonium salt, and specific examples thereof include tetraphenylphosphonium thiocyanate, tetraphenylphosphonium tetra p-methylphenyl borate, and butyltriphenylphosphonium thiocyanate.

The content of the curing accelerator is preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, more preferably 0.1 to 3.0 parts by mass based on 100 parts by mass of the total amount of the maleimide compound (A) and the benzoxazine compound (B) Particularly preferably 1.5 parts by mass. By setting the content of the curing accelerator within this range, the heat resistance of the cured product obtained from the resin composition (P) can be further improved.

The resin composition (P) may contain a coupling agent. The coupling agent may be added directly at the time of preparing the resin composition (P), and if the resin composition (P) contains the inorganic filler (C), it may be added to the inorganic filler (C) in advance. By using the coupling agent, the wettability of the interface between the fiber base or the inorganic filler (C) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the resulting prepreg cured product or resin substrate can be improved.

Examples of the coupling agent include a silane coupling agent such as an epoxy silane coupling agent, a cationic silane coupling agent and an amino silane coupling agent, a titanate coupling agent, and a silicone oil coupling agent. One kind of coupling agent may be used alone, or two or more kinds of coupling agents may be used in combination.

As a result, the wettability of the interface between the fibrous base material or the inorganic filler (C) and each resin can be enhanced, and the resulting cured product of the prepreg and the heat resistance of the resin substrate can be further improved.

As the silane coupling agent, various compounds can be used, and examples thereof include epoxy silane, amino silane, alkyl silane, ureido silane, mercaptosilane, and vinyl silane.

Specific examples of the compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- Ethyl) gamma -aminopropylmethyldimethoxysilane, N-phenyl gamma -aminopropyltriethoxysilane, N-phenyl gamma -aminopropyltrimethoxysilane, N- beta (aminoethyl) Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanone,? -Glycidoxime, N-6- ? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldimethoxysilane,? - - mercaptopropyltrimethoxysilane, methyltrimethoxysilane, gamma -ylidopropyltriethoxysilane, vinyltriethoxysilane Among them, epoxysilane, mercaptosilane and aminosilane are preferable, and aminosilane is preferably a primary amino silane or an aminosilane, An anilinosilane is more preferable.

The amount of the coupling agent to be added is not particularly limited and may be suitably adjusted according to the specific surface area of the inorganic filler (C). When the total solid content of the resin composition (P) is 100 mass% By mass to 1% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less.

When the content of the coupling agent is not less than the lower limit value, the inorganic filler (C) can be sufficiently coated, and the heat resistance of the cured product of the obtained prepreg and the resin substrate can be improved. When the content of the coupling agent is not more than the upper limit value, it is possible to suppress the influence on the reaction, and the deterioration of the cured product of the resulting prepreg and the bending strength of the resin substrate can be suppressed.

To the resin composition (P), additives other than the above components such as a pigment, a dye, a defoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant and an ion scavenger may be added to the resin composition May be added.

Examples of the pigment include inorganic pigments such as kaolin, synthetic iron oxide red, cadmium sulfur, nickel titanium sulfur, strontium sulfur, chromium oxide hydrate, chromium oxide, cobalt aluminum oxide and synthetic ultramarine blue, polycyclic pigments such as phthalocyanine, And the like.

Examples of the dyes include dyes such as isoindolinone, isoindolin, quinophthalone, xanthone, diketopyrrolopyrrole, perylene, perynone, anthraquinone, indigoid, oxazine, quinacridone, , Phthalocyanine, azomethine, and the like.

The resin composition (P) is dissolved and mixed in various organic solvents by using various mixers such as an ultrasonic dispersion system, a high pressure collisional dispersion system, a high-speed rotation dispersion system, a bead mill system, a high-speed shear dispersion system, , And the resin varnish (I) can be obtained by stirring.

Examples of the organic solvent used in the resin varnish (I) include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, Dimethylacetamide, dimethylsulfoxide, ethylene glycol, cellosolve, carbitol, anisole, N-methylpyrrolidone and the like.

The solid content of the resin varnish (I) is not particularly limited, but is preferably 40% by mass or more and 80% by mass or less, particularly preferably 50% by mass or more and 70% by mass or less. This makes it possible to further improve the impregnation property of the resinous varnish (I) to the fiber substrate.

In the above-mentioned resin composition (P), the ratio of each component is, for example, as follows.

(A) is 1.0 mass% or more and 25.0 mass% or less when the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100 mass% Is not less than 1.0 mass% and not more than 25.0 mass%, and the ratio of the inorganic filler (C) is not less than 50.0 mass% and not more than 85.0 mass%.

When the ratio of the maleimide compound (A) is 5.0% by mass or more and 20.0% by mass or less, the proportion of the benzoxazine compound (B) is 2.0% by mass or more and 15.0% by mass or less and the ratio of the inorganic filler (C) And more preferably not less than 80.0 mass%.

Next, the printed wiring board 300 according to the present embodiment will be described. 2 and 3 are cross-sectional views showing an example of the configuration of the printed wiring board 300 in the present embodiment.

The printed wiring board 300 has at least an insulating layer 301 provided with a via hole 307 and a metal layer 303 provided on at least one surface of the insulating layer 301. In the present embodiment, the via hole 307 is a hole for electrically connecting layers, and may be a through hole or a non-through hole.

The printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multilayer printed wiring board as shown in Fig. The double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both surfaces of an insulating layer 301. The multilayer printed wiring board can be formed by a plating through-hole method, a build-up method, or the like on a printed wiring board (not shown) in which two or more metallic layers 303 are laminated on an insulating layer 301 with an interlayer insulating layer to be.

Here, in the printed wiring board 300 according to the present embodiment, the insulating layer 301 corresponds to the insulating layer 301 of the resin substrate or the metal clad laminate 200 according to the present embodiment.

The metal layer 303 is, for example, a circuit layer and has a metal foil 105 and / or an electroless metal plating film 308 and an electrolytic metal plating layer 309.

3, the metal layer 303 is a circuit layer in the core layer 311 or the build-up layer 317. In the case of the multilayer printed circuit board shown in Fig.

The metal layer 303 is formed by SAP (semi-additive process) method on the surface of the metal foil 105 or the insulating layer 301 that has been subjected to, for example, chemical treatment or plasma treatment. After covering the metal foil 105 or the insulating layer 301 with the electroless metal plating film 308, the non-circuit forming portion is protected by the plating resist and the electrolytic metal plating layer 309 is attached by electrolytic plating. Thereafter, the metal layer 303 is formed on the metal foil 105 or the insulating layer 301 by removing the plating resist and removing the electroless metal plating film 308 by flush etching.

The circuit dimension of the metal layer 303 can be 25 μm / 25 μm or less, particularly 15 μm / 15 μm or less when expressed by a line-and-space (L / S) Generally, if the circuit dimensions are made small and fine wiring is formed, insulation reliability between wirings is lowered. However, the printed wiring board 300 according to the present embodiment is capable of fine wiring with a line-and-space (L / S) of 15 mu m / 15 mu m or less and can be miniaturized up to about 10 mu m / 10 mu m in line and space Can be achieved.

The thickness of the metal layer 303 is not particularly limited, but is usually 5 占 퐉 or more and 25 占 퐉 or less.

The insulating layer 305 in the buildup layer 317 is not particularly limited as long as it is made of an insulating material, and can be formed of, for example, a resin film or a prepreg. Of these, prepregs are sheet-like materials and are excellent in various characteristics such as dielectric properties, mechanical and electrical connection reliability under high temperature and humidity, and are suitable for the production of a buildup layer 317 for a printed wiring board.

As the prepreg, the above-mentioned prepreg is particularly preferable.

The thickness of the insulating layer 301 (including the insulating layer 301 in the printed wiring board 300 not including the buildup layer 317) in the core layer 311 is preferably 0.025 mm or more and 0.3 mm or less . When the thickness of the insulating layer 301 is within the above range, the insulating layer 301 is particularly excellent in balance of mechanical strength and productivity, and an insulating layer 301 suitable for a thin printed wiring board can be obtained.

The thickness of the insulating layer 305 in the buildup layer 317 is preferably 0.015 mm or more and 0.05 mm or less. When the thickness of the insulating layer 305 is within the above range, the insulating layer 305 is particularly excellent in balance of mechanical strength and productivity, and an insulating layer 305 suitable for a thin printed wiring board can be obtained.

Next, an example of a method of manufacturing the printed wiring board 300 will be described. However, the manufacturing method of the printed wiring board 300 according to the present embodiment is not limited to the following example.

First, the metal-clad laminate 200 is prepared.

Next, a part or all of the metal foil 105 of the metal clad laminate 200 is removed by etching.

Then, a via hole 307 is formed in the insulating layer 301. The via hole 307 can be formed using, for example, a drill or laser irradiation. Examples of the laser used for laser irradiation include an excimer laser, a UV laser, and a carbon dioxide gas laser. The resin residue or the like after forming the via hole 307 may be removed by an oxidizing agent such as permanganate or bichromate.

The via hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by etching.

Subsequently, the surface of the metal foil 105 or the insulating layer 301 is subjected to chemical treatment or plasma treatment.

The chemical liquid treatment is not particularly limited, and a method of using an oxidant solution or the like having an organic substance decomposing action may, for example, be mentioned. As the plasma treatment, there may be mentioned a method of removing an organic substance residue by irradiating an active species (plasma, radical or the like) having a strong oxidizing action directly on an object.

Then, a metal layer 303 is formed. The metal layer 303 may be formed, for example, by a semi-additive process (SAP) or a modified semi-additive process (MSAP). Hereinafter, this will be described in detail.

First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307 using the electroless plating method, and the electroless metal plating film 308 is formed on the both surfaces of the printed wiring board 300 . The via hole 307 can be suitably filled with a conductive paste or a resin paste. An example of the electroless plating method will be described. For example, first, a catalyst nucleus is provided on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307. The catalyst nucleus is not particularly limited, and for example, noble metal ions and palladium colloid can be used. Subsequently, using this catalyst nuclei as nuclei, an electroless metal plating film 308 is formed by electroless plating. For the electroless plating treatment, for example, a solution containing copper sulfate, formalin, a complexing agent, sodium hydroxide and the like can be used. Further, it is preferable that after the electroless plating, a heat treatment at 100 to 250 ° C is performed to stabilize the plating film. The heat treatment at 120 to 180 占 폚 is particularly preferable in that a coat capable of inhibiting oxidation can be formed. The average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

Subsequently, a plating resist having a predetermined opening pattern is formed on the metal foil 105 and / or the electroless metal plating film 308. This opening pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited and a known material can be used, and liquid and dry films can be used. In the case of fine wiring formation, a photosensitive dry film or the like is preferably used as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, the non-circuit forming area is exposed and photocured, and the unexposed area is dissolved and removed as a developer. By leaving a cured photosensitive dry film, a plating resist is formed.

Subsequently, an electrolytic metal plating layer 309 is formed by electroplating at least on the metal foil 105 and / or the electroless metal plating film 308 in the opening pattern of the plating resist. The electroplating treatment is not particularly limited, and a known method used in a conventional printed wiring board can be used. For example, the metal-clad laminate 200 treated as described above is immersed in a plating solution such as copper sulfate A method of flowing a current through the plating liquid can be used. The electrolytic metal plating layer 309 may be a single layer or a multilayer structure. The material of the electrolytic metal plating layer 309 is not particularly limited. For example, at least one of copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold and solder can be used.

Subsequently, the plating resist is removed using an alkaline removing solution, sulfuric acid, or a commercially available resist removing solution.

Subsequently, the metal foil 105 and / or the electroless metal plating film 308 other than the region where the electrolytic metal plating layer 309 is formed are removed. For example, the metal foil 105 and / or the electroless metal plating film 308 can be removed by using soft etching (flush etching) or the like. Here, the soft-etching treatment can be performed by, for example, etching using an etching solution containing sulfuric acid and hydrogen peroxide. Thus, the metal layer 303 can be formed. The metal layer 303 is constituted by the metal foil 105 and / or the electroless metal plating film 308 and the electrolytic metal plating layer 309.

Further, multilayering can be achieved by repeating the steps of laminating the build-up layer 317 on the printed wiring board 300 as needed, and interlayer connection and circuit formation by a semi-additive process.

Thus, the printed wiring board 300 of the present embodiment is obtained.

Next, the semiconductor device 400 according to the present embodiment will be described. 4 and 5 are sectional views showing an example of the configuration of the semiconductor device 400 in the present embodiment. The printed wiring board 300 can be used for the semiconductor device 400 shown in Figs. 4 and 5. The manufacturing method of the semiconductor device 400 is not particularly limited, and for example, the following method is available.

First, the printed wiring board 300 obtained by the above-described method is prepared. Next, a buildup layer is laminated on the metal layer 303 (circuit layer) of the printed wiring board 300 as necessary, and the process of forming interlayer connection and circuit formation by a semiadditive process is repeated. If necessary, the solder resist layer 401 is laminated on both sides or one side of the printed wiring board 300.

The method of forming the solder resist layer 401 is not particularly limited, and examples thereof include a method in which a dry film type solder resist is formed by laminating, followed by exposure and development, Followed by patterning by exposure and development.

Then, the semiconductor element 407 is mounted on the connection terminal, which is a part of the circuit layer of the printed wiring board 300, with the solder bumps 410 interposed therebetween. Next, the semiconductor element 407 is fixed on the connection terminal via the solder bumps 410 by performing the reflow process. Thereafter, the semiconductor device 407, the solder bumps 410, and the like are sealed with the sealing material 413 to obtain the semiconductor device 400 as shown in Figs. 4 and 5.

Although the embodiments of the present invention have been described above, they are examples of the present invention, and various configurations other than the above may be employed. For example, although the case where the prepreg is one layer is shown in this embodiment mode, an insulating layer in which two or more prepregs are laminated may be produced.

In the above embodiment, the circuit elements of the semiconductor element 407 and the printed wiring board 300 are connected by the solder bumps 410, but the invention is not limited thereto. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by a bonding wire.

Example

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "part" means "part by mass" unless otherwise specified. The respective thicknesses are shown by the average film thicknesses.

In the examples and comparative examples, the following materials were used.

(BMI-2300, manufactured by Daiwa Kasei Kogyo Co., Ltd.) in which n ₁ is 0 or more and 3 or less, X ₁ is a group represented by "-CH ₂ -", a is 0, Priest, Mw = 750)

Maleimide compound 2: bisphenol A diphenylether bis maleimide (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

Maleimide compound 3: 4,4'-diphenylmethane bismaleimide (In the formula (1), n ₁ is 0, X ₁ is a group represented by "-CH ₂ -", a is 0, b is 0 Phosphorus compound, BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd.)

Maleimide compound 4: 1,6'-bismaleimide- (2,2,4-trimethyl) hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co.)

Maleimide compound 5: imide-extended bismaleimide (BMI-1500, bismaleimide compound represented by formula (a1), manufactured by Designer Molecules, molecular weight 1500)

Cyanate ester resin: bisphenol A dicyanate prepolymer (MEK solution of solid content 75% by mass, BA230S manufactured by Lonza)

Benzoxazine compound 1: A benzoxazine compound (P-d type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.) represented by the formula (2-1)

Benzoxazine compound 2: The benzoxazine compound represented by formula (3-1) (F-a type benzoxazine, manufactured by Shikoku Chemical Industry Co., Ltd.)

Epoxy resin 1: Aralik type epoxy resin (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)

Epoxy resin 2: Bisphenol F type epoxy resin (EPICLON 830S, manufactured by DIC)

Epoxy resin 3: Naphthalene diol type epoxy resin (EPICLON HP-4032D, manufactured by DIC)

Epoxy resin 4: Silsesquioxane type epoxy resin (Konfoselen SQ502-8, manufactured by Arakawa Chemical Industries, Ltd.)

Phenol resin 1: novolac phenolic resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)

Inorganic filler 1: silica (SC4050, product of Admatex, average particle size 1.1 mu m, silica slurry treated with phenylamino silane)

Low stress material 1: Carboxylic acid-terminated acrylonitrile-butadiene rubber (CTBN1008SP, manufactured by PTI Japan)

Low stress material 2: amino group end acrylonitrile / butadiene rubber (PTI Japan, ATBN1300X16)

Low stress material 3: silicone compound (epoxy cross-linked three-dimensional cross-linked silicone resin containing epoxy group and phenyl group, manufactured by Dow Corning Toray, AY42-119)

Low stress material 4: Silicone compound (silicone epoxy resin, BY16-115, Dow Corning Toray Co., Ltd.)

Low stress material 5: Silicone compound (denatured silicone resin having amino groups at both ends of molecular chain, BY16-853, manufactured by Dow Corning Toray Co., Ltd.)

Low stress material 6: acrylic block copolymer (PMMA-b-PBA-b-PMMA; b = block, number average molecular weight: about 10,000, Aramemase, Nano Strength M51)

Curing accelerator 1: 2-phenylimidazole (Shikoku Chemicals, 2PZ-PW)

Curing accelerator 2: Tetraphenylphosphonium tetra-p-tolyl borate (TPP-MK manufactured by Hokko Chemical Industry Co., Ltd.)

Next, the production of the prepreg will be described. The composition of the resin varnish used is shown in Table 1 (parts by mass), and the evaluation results and the like of the obtained prepregs 1 to 22 are shown in Table 2. In Table 2, P1 to P20 refer to prepreg 1 to prepreg 22.

[1] prepreg 1

1. Preparation of resin varnish 1

A mixed solution prepared by dissolving or dispersing each component at a solid content ratio shown in Table 1 and adjusting it to methyl ethyl ketone to a non-volatile content of 70 mass% was prepared. Thereafter, this mixed solution was stirred using a high-speed stirring device to prepare resin varnish 1.

2. Preparation of prepreg

(Prepreg 1)

Glass woven fabric (cross type # 2118, T glass, basis weight 114 g / m ² ) was impregnated with resin varnish 1 with a coating device. Thereafter, the glass woven fabric was dried for 10 minutes by a hot air dryer at 140 캜 to obtain a prepreg 1 (P1) having a thickness of 107 탆.

(Prepregs 2 to 22)

Prepregs 2 to 22 were produced in the same manner as prepreg 1 except that the resin varnishes were changed as shown in Table 1. [ However, the varnish 19 adjusted the solid content concentration with dimethylformamide from the viewpoint of solubility.

(Example 1)

1. Manufacturing of Resin Substrate

On both sides of the prepreg 1, an ultra-thin copper foil (Microsin Ex, manufactured by Mitsui Kinzoku Kogyo Co., Ltd., 2.0 m) was laminated. Next, the resultant was heated and pressed at 4 MPa and 230 DEG C for 2 hours to obtain a resin substrate. The thickness of the obtained core layer (a portion made of resin substrate) of the obtained resin-coated metal foil was 0.107 mm.

2. Fabrication of printed wiring board

First, the extremely thin copper foil layer on the surface of the resin substrate with a metal foil obtained in the above item was subjected to a coarsening treatment of about 1 mu m. Thereafter, through-holes of? 80 占 퐉 for interlayer connection were formed with a carbon dioxide gas laser. Subsequently, a resin substrate with a metal foil was placed in a container filled with a swelling liquid (manufactured by Artec Japan Co., Swelling Deep Curei Kang P) at 60 ° C and immersed for 5 minutes, and then the resin substrate with a metal foil was taken out of the container. Thereafter, a resin substrate with a metal foil was placed in a container filled with an aqueous solution of gallium permanganate (manufactured by Artec Japan Co., Ltd., Concentrate Compact CP) at 80 ° C, immersed for 2 minutes, neutralized and subjected to desmear treatment in a through hole. Next, the resin substrate with the metal foil after the desmear treatment was subjected to electroless copper plating so as to have a thickness of 0.5 mu m. Next, a resist layer for electrolytic copper plating was formed so as to have a thickness of 18 mu m, and patterned copper plating. Thereafter, it was heated at 150 캜 for 30 minutes to post-cure. Subsequently, the plating resist was peeled off and the whole surface was subjected to flush etching to form a pattern of L / S = 15/15 m.

(Examples 2 to 18 and Comparative Examples 1 to 4)

A resin substrate and a printed wiring board were produced in the same manner as in Example 1, except that the kind of the prepreg was changed as shown in Table 2.

The following evaluations were performed on the resin substrates obtained in the respective Examples and Comparative Examples. The evaluation results are shown in Table 2.

(1) Glass transition temperature

The glass transition temperature was measured using a dynamic viscoelasticity analyzer (DMA apparatus, manufactured by TA Instruments, Inc., Q800).

First, a test piece of 8 mm x 40 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (second iron chloride solution, 35 ° C) to obtain a cured prepreg. Then, the obtained cured product of the prepreg was subjected to dynamic viscoelasticity measurement at a heating rate of 5 캜 / min and a frequency of 1 Hz. Further, the glass transition temperature was set to a temperature at which the tan 隆 exhibited the maximum value at a frequency of 1 Hz.

(2) Storage elastic modulus E '

The storage elastic modulus E 'was measured using a dynamic viscoelasticity analyzer (DMA device, manufactured by TA Instruments, Q800).

First, a test piece of 8 mm x 40 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (second iron chloride solution, 35 ° C) to obtain a cured prepreg.

The cured product of the obtained prepreg was subjected to measurement of the storage elastic modulus at 30 DEG C and 250 DEG C at a heating rate of 5 DEG C / min and a frequency of 1 Hz to obtain a storage elastic modulus E 'at ₃₀ DEG C and a storage elastic modulus E at 250 DEG C ' ₂₅₀ , and E' ₃₀ / E ' ₂₅₀ .

(3) Dimensional Shrinkage

First, a test piece of 4 mm x 15 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (second iron chloride solution, 35 ° C) to obtain a cured prepreg.

Subsequently, the cured product of the obtained prepreg was subjected to a temperature elevation rate of 10 占 폚 / min, a load of 10 g, and a temperature of 30 占 폚 to 260 占 폚 under a compression mode condition using a thermomechanical analyzer TMA (Q400, manufactured by TA Instruments) And holding the sample at 260 DEG C for 1 hour. And it was obtained from a thermal expansion amount L ₂ from the reference length L ₀ when maintained for one hour up to a thermal expansion amount L ₁ and the cured product of the prepreg from the prepreg in the reference length L ₀ of the cured product in 260 ℃. Subsequently, the dimensional shrinkage ratio represented by 100 x (L ₁ -L ₂ ) / L ₀ was calculated.

(4) Coefficient of linear expansion

First, a test piece of 4 mm x 15 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (second iron chloride solution, 35 ° C) to obtain a cured prepreg.

Subsequently, a cured product of the obtained prepreg was subjected to heat treatment at a temperature range of 30 to 260 占 폚, a temperature raising rate of 10 占 폚 / min, a load of 10 g, and a compression mode using a thermomechanical analyzer TMA (TA Instruments Co., Ltd., Q400) Mechanical analysis (TMA) was performed for two cycles. An average value? ₁ of the linear expansion coefficient in the plane direction (XY direction) in the range of 50 to 150 占 폚 and an average value? ₂ of the linear expansion coefficient in the plane direction (XY direction) in the range of 150 to 250 占.

Further, the expansion coefficient was the value of the second cycle.

(5)

First, a test piece of 4 mm x 15 mm was cut out from the obtained resin substrate. Next, the copper foil was removed with an etching solution (second iron chloride solution, 35 DEG C) to obtain a cured prepreg.

Subsequently, the cured product of the obtained prepreg was dried at 120 ° C. for 1 hour to obtain a first mass, and after the cured product was treated under the following conditions, the mass of the cured product after drying at 120 ° C. for 1 hour was changed to a second mass , The amount of reduced film defined by [{(first mass) - (second mass)} / (sum of areas of both sides of the cured product) × 100] was calculated.

<Condition>

The cured product was immersed in a 3 g / L sodium hydroxide solution (solvent: diethylene glycol monobutylether 11.1 vol%, ethylene glycol 3.6 vol%, pure water 85.3 vol%) at 60 DEG C for 5 minutes to swell the cured product . Subsequently, the swollen cured product is dipped in a harmony treatment aqueous solution (60 g / L of sodium permanganate and 45 g / L of sodium hydroxide) at 80 DEG C for 5 minutes to coarsen the cured product. Subsequently, the cured product subjected to the roughening treatment is immersed in a neutralizing solution (98 mass% sulfuric acid 5.0 volume%, sulfuric acid hydroxylamine 0.8 volume%, pure water 94.2 volume%) at 40 ° C for 5 minutes to neutralize the cured product

(6) Dimensional change rate

First, a test piece of 4 mm x 15 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (second iron chloride solution, 35 ° C) to obtain a cured prepreg.

Subsequently, a cured product of the obtained prepreg was subjected to compression molding at a temperature elevation rate of 10 占 폚 / min, a load of 10 g, and a compression mode using a thermomechanical analyzer TMA (TA Instruments Co., Ltd., Q400) And a thermomechanical analysis measurement was carried out with a process of raising the temperature from 300 DEG C to 30 DEG C at a rate of 10 DEG C / min. Then, the length in the longitudinal direction of the cured product before the thermomechanical analysis measurement was measured as the reference length L _0, and the length L ₁ in the longitudinal direction of the cured product at 30 캜 in the process of lowering the temperature. Subsequently, the dimensional change rate, which is represented by 100 x (L ₁ -L ₀ ) / L ₀ , was calculated from the obtained L ₀ and L ₁ .

(7) Peel strength change rate

The rate of change in peel strength, which is expressed by 100 x (P ₁ -P ₂ ) / P ₁ when the resin substrate (metal-clad laminate) was stored for 100 hours under the environment of 135 ° C and 85% RH was calculated.

In the above formula, P ₁ is the peel strength between the cured product of the prepreg and the metal foil measured according to JIS C-6481: 1996 before storage. P ₂ is the peel strength between the cured product of the prepreg and the metal foil measured according to JIS C-6481: 1996 after storage.

(8) Three-wire insulation reliability evaluation

A buildup material (BLA-3700GS made by Sumitomo Bakelite Co., Ltd.) was laminated on a fine circuit pattern of L / S = 15/15 占 퐉 of a printed wiring board, and then a cured test sample was prepared. Using this test sample, the continuous-wet insulation resistance was evaluated under conditions of 130 ° C, humidity 85%, and an applied voltage of 3.3 V. Also, the resistance value was set to 10 ⁶ Ω or less. The evaluation criteria are as follows.

○: No failure for 500 hours or more

△: Failure in less than 200 to 500 hours

×: Failure in less than 200 hours

(9) Evaluation of fine line workability

The fine line workability of a printed wiring board after forming a fine circuit pattern of L / S = 15/15 占 퐉 was evaluated by a laser microscope by appearance inspection and conduction check of a fine line (circuit). The evaluation criteria are as follows.

◎: Shape of fine wire, no problem in all conduction

○: Although there is a problem in the shape of a part of the thin wire, there is no short circuit, wiring short-circuit,

×: Short, wiring short-circuited

(10) Through hole insulation reliability evaluation

In the production of the above-mentioned printed wiring board, 20 pairs of through holes of? 80 占 퐉 in interlayer connection were formed so as to be 80 占 퐉 between the walls. Next, a buildup material (BLA-3700GS made by Sumitomo Bakelite Co., Ltd.) was laminated on the circuit pattern, and then a cured test sample was produced. Using this test sample, the continuous-wet insulation resistance was evaluated at 130 ° C, a humidity of 85%, and an applied voltage of 5.5 V. Also, the resistance value was set to 10 ⁶ Ω or less. The evaluation criteria are as follows.

◎: No breakdown for 500 hours (Good)

○: Failure occurred in less than 200 to 500 hours (no problem in practical terms)

△: Failure occurred in less than 200 hours (practically unusable)

X: Failure in less than 100 hours (not available)

(11) Evaluation of bending of semiconductor device

A buildup material (BLA-3700GS, made by Sumitomo Bakelite Co., Ltd.) was laminated on the printed wiring board after the circuit pattern was formed, and then cured. Next, this cured product was subjected to circuit processing by the semi-additive method. A semiconductor device with a solder bump having a length of 10 mm, a width of 10 mm, and a thickness of 100 占 퐉 was mounted thereon. Next, the semiconductor device was sealed with underfill (manufactured by Sumitomo Bakelite Co., Ltd., CRP-4160G) and cured at 150 占 폚 for 2 hours. Finally, the semiconductor device was diced into 15 mm x 15 mm.

The bending of the obtained semiconductor device at 260 캜 was evaluated using a temperature-variable laser three-dimensional measuring instrument (manufactured by Hitachi, Ltd., model LS220-MT100MT50). The evaluation was carried out by placing a semiconductor device in the sample chamber of the measuring instrument with the semiconductor element surface facing downward. The displacement in the height direction was measured, and the value with the greatest displacement difference was taken as the deflection amount. The evaluation criteria are as follows.

?: Less than 30 占 퐉

?: Deflection of 30 占 퐉 or more and less than 50 占 퐉

X: Deflection of 50 占 퐉 or more

(12) Heat cycle test

First, four semiconductor devices obtained in (11) were prepared. These semiconductor devices were treated for 168 hours under the conditions of 85 캜 and 85% RH, and then treated three times at IR reflow (peak temperature: 260 캜). Thereafter, one cycle was performed under the conditions of -55 占 폚 (15 minutes) and 125 占 폚 (15 minutes) in the atmosphere, and these conditions were repeated for 500 cycles. Next, by using an ultrasonic imaging apparatus (FS300, manufactured by Hitachi Genki Fine-Tex), it was observed that there was no abnormality in the semiconductor element and the solder bump.

◎: No abnormality in both semiconductor element and solder bump

O: Cracks were found in a part of the semiconductor element and / or the solder bump, but there was no practical problem

C: Cracks were found in part or all of the semiconductor element and / or the solder bump, causing practical problems

[Table 1]

[Table 2]

105 metal foil
200 metal-clad laminate
300 printed wiring board
301 insulating layer
303 metal layer
305 insulating layer
307 via hole
308 Electroless metal plating film
309 Electrolytic metal plating layer
311 core layer
317 buildup layer
400 semiconductor device
401 solder resist layer
407 Semiconductor device
410 solder bump
413 Sealing material

Claims (15)

A prepreg obtained by impregnating a fiber substrate with a thermosetting resin composition,
The cured product obtained by subjecting the prepreg to heat treatment at 230 占 폚 for 2 hours is subjected to thermomechanical analysis to measure the average coefficient of linear expansion? ₁ in the in-plane direction of the cured product in the range of 50 占 폚 to 150 占 폚 Wherein a ratio (α ₂ / α ₁ ) of an average linear expansion coefficient α ₂ calculated in the range of 150 ° C. to 250 ° C. is 0.7 or more and 2.0 or less and the average linear expansion coefficient α ₂ is 8.0 ppm / . The method according to claim 1,
The prepreg is heat treated at 230 ° C for 2 hours, and the resulting cured product is subjected to thermomechanical analysis with a process of raising the temperature from 30 ° C to 260 ° C at a rate of 10 ° C / min and holding the process at 260 ° C for one hour When doing so,
1 hour the thermomechanical analysis of the cured length relative to the length of the water vertically as L ₀ and, and the maximum thermal expansion of from the reference length of the cured product of L ₀ to L _1, the cured product before measurement at 260 ℃ And the amount of thermal expansion from the reference length L ₀ at the time of holding is L ₂ ,
100 占 (L ₁ -L ₂ ) / L ₀ is 0.15% or less. The method according to claim 1,
A step of raising the temperature of the cured product obtained by heating the prepreg at 230 ° C for 2 hours from 30 ° C to 300 ° C at a rate of 10 ° C / min and a step of decreasing the temperature from 300 ° C to 30 ° C at a rate of 10 ° C / When the thermomechanical analysis measurement in the plane direction in the compression mode is performed,
The longitudinal length of the cured product before the thermomechanical analysis measurement is defined as a reference length L ₀ ,
When the longitudinal length of the cured product at 30 DEG C in the step of cooling down is L &_lt; _{1 &gt};
100 占 (L ₁ -L ₀ ) / L ₀ is -0.20% or more. The method according to claim 1,
Wherein the cured product has a glass transition temperature of 260 占 폚 or more when subjected to dynamic viscoelasticity measurement under the conditions of a temperature rise rate of 5 占 폚 / min and a frequency of 1 Hz. The method according to claim 1,
With respect to the cured product, when performing the dynamic viscoelasticity measurement, the "storage elastic modulus E at 30 ℃ about _{250 '30} ratio (E' ₃₀ / E _'250) of the storage modulus E at the curing 250 ℃ water, 1.05 or more and 1.75 or less. The method according to claim 1,
Wherein a thickness of the prepreg is not less than 20 占 퐉 and not more than 220 占 퐉. The method according to claim 1,
Wherein the thermosetting resin composition comprises a maleimide compound (A), a benzoxazine compound (B), and an inorganic filler (C). The method of claim 7,
Wherein the maleimide compound (A) comprises a maleimide compound (A1) represented by the following formula (1).
[Chemical Formula 1]

(1), n ₁ is an integer of 0 or more and 10 or less, X ₁ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (1a), a group represented by the formula: -SO ₂ - , A group represented by "-CO-", an oxygen atom or a single bond, R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms and a is independently an integer of 0 to 4 , and b are each independently an integer of 0 or more and 3 or less)
(2)

(In the formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 to 30 carbon atoms and n ₂ is an integer of 0 or more) The method of claim 7,
Wherein the benzoxazine compound (B) comprises at least one compound selected from a compound represented by the following formula (2) and a compound represented by the following formula (3).
(3)

(2), each X ₂ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula "-SO ₂ -", a group represented by "-CO-" An oxygen atom or a single bond, R ₂ is independently a hydrocarbon group having 1 to 6 carbon atoms, and each c is independently an integer of 0 to 4)
[Chemical Formula 4]

(3), each X ₃ independently represents an alkylene group having 1 to 10 carbon atoms, a group represented by the formula (1a), a group represented by the formula "-SO ₂ -", a group represented by "-CO-" An oxygen atom or a single bond, R ₃ is independently a hydrocarbon group having 1 to 6 carbon atoms, and d is independently an integer of 0 or more and 4 or less) The method of claim 7,
Wherein the inorganic filler (C) comprises at least one selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide. A resin substrate comprising a cured product of a prepreg according to any one of claims 1 to 10. A metal-clad laminate provided with a metal foil on one side or both sides of a cured product of a prepreg according to any one of claims 1 to 10, or on one side or both sides of a cured product of a laminate obtained by superimposing two or more prepregs. The method of claim 12,
When the metal-clad laminate was stored for 100 hours under an environment of 135 ° C and a humidity of 85% RH,
The peel strength between the cured product of the prepreg and the metal foil measured according to JIS C-6481: 1996 before storage is defined as P ₁ ,
When the peel strength between the cured product of the prepreg and the metal foil, which is measured according to JIS C-6481: 1996 after storage, is P ₂ ,
100 占 (P ₁ -P ₂ ) / P ₁ is 30% or less. A printed wiring board obtained by circuit processing a resin substrate according to Claim 11 or a metal-clad laminate according to Claim 12, wherein the printed wiring board has one or more circuit layers. A semiconductor device in which a semiconductor element is mounted on the circuit layer of a printed wiring board according to claim 14

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