TW201700565A - Prepreg, resin substrate, metal clad laminated board, printed wiring board and semiconductor device - Google Patents

Abstract

A prepreg of the present invention is formed by impregnating a thermosetting resin composition into a fiber base material. When a thermomechanical analysis measurement is performed on a cured product obtained by heating the prepreg at 230 DEG C for 2 hours, a ratio "[alpha]2"/"[alpha]1" of a mean coefficient of linear expansion "[alpha]2" of the cured product in an in-plane direction thereof calculated within 150 to 250 DEG C to a mean coefficient of linear expansion "[alpha]1" of the cured product in the in-plane direction thereof calculated within 50 to 150 DEG C is in the range of 0.7 to 2.0, and the mean coefficient of linear expansion "[alpha]2" is 8.0 ppm/DEG C or less.

Description

Prepreg, resin substrate, metal-clad laminate, printed wiring substrate, and semiconductor Device

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

In recent years, with the demand for high performance of electronic equipment, high-density integration and high-density mounting of electronic components are being carried out. In addition, due to the high-density integration and high-density mounting of electronic components, the miniaturization of semiconductor devices using such electronic devices has progressed rapidly. Further, a printed wiring 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 is proposed. The SAP method performs a roughening treatment on the surface of the insulating layer to form an electroless metal plating film as a substrate on the surface of the insulating layer. Next, the non-circuit forming portion is protected by the plating resist, and the copper of the circuit forming portion is thickened by plating. Next, the plating resist is removed, and thereafter, the metal-free plating layer other than the circuit formation portion is removed by rapid etching to form a circuit on the insulating layer. According to the SAP method, since the metal layer deposited on the insulating layer can be made thinner, a finer circuit wiring can be formed.

The semiconductor device is formed, for example, by mounting a semiconductor element on a printed wiring board. As a technique of such a printed wiring board, the technique described in the following patent document 1 is mentioned, for example. Patent Document 1 describes a printed wiring board using a substance containing dihydrobenzobenzene. A thermosetting resin composition containing a thermosetting resin of a ring and a thermosetting resin having a maleimide ring as an essential component. In such a thermosetting resin composition, the content ratio of the thermosetting resin having a maleimide ring is relative to having a dihydrobenzoyl group The total amount of the thermosetting resin of the ring and the thermosetting resin having a maleimide ring is 3 to 30% by weight.

[Prior patent documents] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-259248

In a semiconductor device formed by mounting a semiconductor element on a printed wiring board, insulation reliability between wirings is required to be excellent. Such a request is particularly remarkable as the wiring of the printed wiring board is increased in density in recent years. Therefore, according to the research by the inventors of the present invention, it is apparent that the technique described in Patent Document 1 is difficult to sufficiently obtain the insulation reliability of the printed wiring board under high temperature and high humidity.

According to the present invention, a prepreg is provided in which a thermosetting resin composition is impregnated into a fibrous base material, and a cured product obtained by heat-treating the prepreg at 230 ° C for 2 hours is subjected to the treatment. In the thermomechanical analysis, the average linear expansion coefficient α ₂ calculated in the in-plane direction of the hardened material in the range of 150 ° C to 250 ° C is relative to the average linear expansion coefficient α ₁ calculated in the range of 50 ° C to 150 ° C. The ratio (α ₂ /α ₁ ) is 0.7 or more and 2.0 or less, and the average linear expansion coefficient α ₂ is 8.0 ppm/° C. or less.

Furthermore, according to the present invention, there is provided a resin substrate comprising the cured product of the prepreg.

Furthermore, according to the present invention, there is provided a metal-clad laminate which is provided on one side or both sides of a cured product of the prepreg or a single side of a cured product in which the prepreg is superposed on two or more layers. Double-sided, made of metal foil.

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

Furthermore, according to the present invention, a semiconductor device is provided 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 which can realize a printed wiring board having a fine circuit size and excellent insulation reliability under high temperature and high humidity. Further, it is possible to provide a printed wiring board and a semiconductor device which are excellent in insulation reliability under high temperature and high humidity.

105‧‧‧metal foil

200‧‧‧Metal covered laminate

300‧‧‧Printed wiring substrate

301‧‧‧Insulation

303‧‧‧metal layer

305‧‧‧Insulation

307‧‧‧through hole

308‧‧‧Electroless metal plating film

309‧‧‧Electrometal plating film

311‧‧‧ core layer

317‧‧‧Additional layer

400‧‧‧Semiconductor device

401‧‧‧solder resistance layer

407‧‧‧Semiconductor components

410‧‧‧ solder bumps

413‧‧‧ Sealing material

Fig. 1 is a cross-sectional view showing an example of a configuration of a metal-clad laminate according to the embodiment.

Fig. 2 is a cross-sectional view showing an example of a configuration of a printed wiring board of the embodiment.

3 is a cross-sectional view showing an example of a configuration of a printed wiring board of the embodiment.

4 is a cross-sectional view showing an example of the configuration of a semiconductor device of the embodiment.

Fig. 5 is a cross-sectional view showing an example of a configuration of a semiconductor device of the embodiment.

Embodiments of the present invention will be described below using the drawings. In the drawings, the same constituent elements are denoted by the common symbols, and the description is omitted as appropriate. Moreover, the figure is a schematic view and does not coincide with the actual size ratio. Further, unless otherwise specified, the "~" between the numbers in the text indicates the above to the following.

First, the prepreg of this embodiment will be described.

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

Further, the resin substrate is used to form 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 heat-hardening one sheet of the prepreg. Further, the resin substrate can also be obtained by heat-hardening a laminate of two or more prepreg layers. Further, as the resin substrate, a layer composed of a fibrous base material constituting the prepreg and an insulating material other than the resin composition (P) may be provided on one surface or both surfaces of the prepreg. As such a layer, for example, a hard coat layer for improving the scratch resistance of the resin substrate can be mentioned. The resin substrate having a hard coat layer can be obtained, for example, by adhering the hard coat layer to one side or both sides of the cured product of the above prepreg via the undercoat layer. Further, the prepreg may be hardened according to the state in which the hard coat layer is adhered to one or both sides of the prepreg before curing, and the prepreg is adhered to the hard coat layer. A resin substrate can be obtained.

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

In the case where the prepreg is used to form an insulating layer in the core layer in the printed wiring board, for example, two or more prepregs are overlapped, and the obtained laminate is heat-hardened. Thereby, an insulating layer for the core layer can also be formed.

The prepreg system satisfies the following conditions from the viewpoint of improving the insulation reliability of the printed wiring board under high temperature and high humidity or the connection reliability between the semiconductor element and the printed wiring board. In other words, the cured product obtained by heat-treating the prepreg at 230 ° C for 2 hours (hereinafter also referred to as "cured material" for short) is subjected to thermomechanical analysis, and the in-plane direction of the cured product is 150 ° C to 250 ° C. the calculated average linear expansion coefficient within a range of α ₂ with respect ℃ average linear expansion coefficient in the range of 50 to 150 ℃ ℃ the calculated ratio of the [alpha] ₁ (α ₂ / α ₁₎ is 0.7 or more and 2.0 or less. Further, α ₂ /α _{1 is} preferably 0.75 or more and 1.5 or less, more preferably 0.8 or more and 1.2 or less.

Further, the cured product of the prepreg may be obtained by simply heating the prepreg at a predetermined temperature (230 ° C), but is preferably a cured product obtained by heating under a pressurized condition. This is a cured product formed by heating and pressurizing the prepreg, and the physical properties thereof are more stable, and the correct physical property evaluation can be performed. In the case where the prepreg is heated and pressurized to form a cured product, for example, by heating and pressurizing at 4 MPa and 230 ° C for 2 hours, a cured product can be obtained.

Further, the resin substrate composed only of the cured product of the prepreg satisfies the same conditions as those of the cured product of the prepreg described above. Moreover, 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 conditions listed as the conditions of the cured product of the prepreg are also the conditions to be satisfied by the cured product of the prepreg of the resin substrate.

In the present embodiment, the average linear expansion coefficients α ₁ and α ₂ are TMA (thermo-mechanical analysis) devices (Q400 manufactured by TA Instruments Co., Ltd.), and the temperature range is 30 ° C to 260 ° C and the temperature increase rate is 10 ° C for the object. The average value of the linear expansion coefficient (CTE) in the plane direction (XY direction) is measured by the condition of /min, the load of 10 g, and the compression mode.

In the cured product, when α ₂ /α ₁ satisfies the above range, even if the environmental temperature of the obtained printed wiring board largely changes, the stress change caused by the difference in linear expansion coefficient between the circuit layer and the insulating layer can be reduced. Therefore, even when the obtained printed wiring board or semiconductor device is placed for a long period of time, the adhesion between the circuit layer and the insulating layer can be maintained. From the above, it is considered that by using such a prepreg, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved.

Further, when α ₂ /α ₁ satisfies the above range in the cured product, even if the ambient temperature of the obtained semiconductor device largely changes, the difference in linear expansion coefficient between the printed wiring board and the semiconductor element can be reduced. Stress changes. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the insulation reliability or temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

Moreover, the prepreg system further satisfies the following conditions from the viewpoint of further improving the insulation reliability of the printed wiring board under high temperature and high humidity or the connection reliability between the semiconductor element and the printed wiring board. That is, when the cured product is subjected to thermomechanical analysis, the average linear expansion coefficient α ₂ calculated in the in-plane direction of the cured product in the range of 150 ° C to 250 ° C is 8.0 ppm / ° C or less. Further, the average linear expansion coefficient α _{2 is} preferably 7.5 ppm/° C. or less, and particularly preferably 7.2 ppm/° C. or less. The lower limit is not particularly limited and may be, for example, 0.1 ppm/° C. or more.

In the cured product, when the average linear expansion coefficient α ₂ satisfies the above range, even if the obtained printed wiring board is exposed to a high temperature such as solder reflow, the difference in linear expansion coefficient between the circuit layer and the insulating layer can be reduced. stress. Therefore, even when the obtained printed wiring board or semiconductor device is placed for a long period of time, the adhesion between the circuit layer and the insulating layer can be maintained. Thereby, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved.

Further, in the cured product, if the average linear expansion coefficient α ₂ satisfies the above range, even if the obtained semiconductor device is exposed to a high temperature such as solder reflow, the difference in linear expansion coefficient between the printed wiring board and the semiconductor element can be reduced. The resulting stress. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the insulation reliability or temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

Moreover, from the viewpoint of improving the insulation reliability of the printed wiring board under high temperature and high humidity or the connection reliability between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the following conditions. That is, when the cured product is subjected to thermomechanical analysis, the average linear expansion coefficient α ₁ calculated in the in-plane direction of the cured product in the range of 50 ° C to 150 ° C is 7.5 ppm / ° C or less, preferably 7.2 ppm / Below °C, especially below 6.5ppm/°C. The lower limit is not particularly limited and may be, for example, 0.1 ppm/° C. or more.

In the cured product, if the average linear expansion coefficient α ₁ satisfies the above range, even if the ambient temperature of the obtained printed wiring board largely changes, the stress generated by the difference in linear expansion coefficient between the circuit layer and the insulating layer can be reduced. Therefore, even when the obtained printed wiring board or semiconductor device is placed for a long period of time, the adhesion between the circuit layer and the insulating layer can be maintained. Thereby, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved.

Further, in the cured product, if the average linear expansion coefficient α ₁ satisfies the above range, even if the obtained semiconductor device is exposed to a high temperature, the difference in linear expansion coefficient between the printed wiring board and the semiconductor element can be reduced. stress. As a result, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the insulation reliability or temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

In order to achieve such an average linear expansion coefficient α ₁ or α ₂ , α ₂ /α ₁ , it is important to appropriately set the type of the constituent component of the resin composition (P) of the prepreg or the amount of each component, and the prepreg. Manufacturing method, etc. Further, the constituent component of the resin composition (P) is specifically a maleimide compound (A) to be described later, and a benzo compound. Compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fibrous substrate, hardening accelerator, and the like.

Moreover, from the viewpoint of further improving the connection reliability between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the above conditions. That is, in the case of a hardened material, a thermomechanical analysis device is used to perform a thermomechanical analysis having a temperature rising from 30 ° C to 260 ° C at 10 ° C/min and a process of maintaining at 260 ° C for 1 hour. The length of the cured product before the mechanical analysis and measurement is set to the reference length L ₀ , and the maximum amount of thermal expansion from the reference length L ₀ of the cured product is L ₁ , and the cured product is kept at 260 ° C for 1 hour. When the amount of thermal expansion from the reference 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 is not particularly limited and may be, for example, 0.00% or more.

Further, the longitudinal direction of the cured product refers to the conveying direction of the prepreg (so-called MD).

In general, 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 fiber base material when the prepreg is heat-cured) is released, and the insulating layer is shrunk. Further, when it is cooled from a high temperature to a normal temperature, the resin component of the insulating layer shrinks. On the other hand, when the dimensional shrinkage ratio satisfies the above range in the cured product, when the obtained semiconductor device is exposed to a high temperature, the stress generated by the shrinkage of the insulating layer in the printed wiring board can be reduced. Therefore, the insulating layer and the circuit layer can be maintained even when the obtained semiconductor device is placed for a long period of time in which the temperature changes drastically. The tightness between the two. As a result, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved. Moreover, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

In order to achieve such dimensional shrinkage, it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituent components of the resin composition (P), respectively. The type or amount of the compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material (E), the fiber base material, the curing accelerator, and the like, the method for producing the prepreg, and the like.

Further, in the compression mode in which the cured product is subjected to a temperature rising process from 30 ° C to 300 ° C at 10 ° C / min and a temperature decrease from 300 ° C to 30 ° C at 10 ° C / min using a thermomechanical analyzer. In the thermomechanical analysis of the surface direction, the length in the longitudinal direction of the cured product before the thermomechanical analysis is taken as the reference length L ₀ , and the length in the longitudinal direction of the cured product at 30 ° C in the cooling process is set to L ₁ . The dimensional change ratio represented by 100 × (L _{1 -} L ₀ ) / L ₀ is preferably -0.20% or more, more preferably -0.15% or more. The lower limit is not particularly limited and may be, for example, 0.00% or less.

Further, the longitudinal direction of the cured product refers to the conveying direction of the prepreg (so-called MD).

In the cured product, when the dimensional change rate satisfies the above range, when the obtained semiconductor device is exposed to a drastic temperature change, the stress generated by the dimensional change of the insulating layer in the printed wiring board can be reduced. Therefore, even when the obtained semiconductor device is placed for a long period of time, the adhesion between the insulating layer and the circuit layer can be maintained. As a result, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be further improved. Moreover, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and temperature cycle reliability between the semiconductor element and the printed wiring board at a high temperature can be further improved.

In order to achieve such a dimensional change rate, it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituent components of the resin composition (P), respectively. The type or amount of the compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material (E), the fiber base material, the curing accelerator, and the like, the method for producing the prepreg, and the like.

Further, from the viewpoint of improving the rigidity or heat resistance of the obtained printed wiring board, the prepreg preferably satisfies the following conditions. That is, when the dynamic viscoelasticity measurement is performed on the cured product at a temperature rising rate of 5 ° C/min and a frequency of 1 Hz, the glass transition temperature of the cured product is preferably 260 ° C or higher, more preferably 270 ° C or higher, and still more preferably 280. Above °C. The upper limit is preferably 400 ° C or lower. The glass transition temperature can be measured using a dynamic viscoelasticity analyzer (DMA).

When the glass transition temperature of the cured product measured by the dynamic viscoelasticity measurement satisfies the above range, the rigidity of the obtained printed wiring board can be improved, and the warpage of the printed wiring board at the time of mounting can be further reduced. As a result, in the obtained semiconductor device, the positional deviation of the semiconductor element with respect 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, it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituents of the resin composition (P), respectively. The type or amount of the compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material (E), the fiber base material, the curing accelerator, and the like, the method for producing the prepreg, and the like.

In addition, from the viewpoint of further improving the balance of 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 the cured product is subjected to dynamic viscoelasticity measurement, the storage elastic modulus E' _{30 of the} cured product at 30 ° C is preferably 10 GPa or more, more preferably 20 GPa or more. The upper limit is not particularly limited, and may be, for example, 40 GPa or less.

When the storage elastic modulus E' ₃₀ of the cured product at 30 ° C satisfies the above range, the balance of the rigidity, heat resistance, and stress relaxation ability of the obtained printed wiring board can be improved, and the printed wiring board at the time of mounting can be further reduced. Warping. Therefore, with respect to the obtained semiconductor device, the positional deviation of the semiconductor element with respect to the printed wiring board can be further suppressed. As a result, the connection reliability between the semiconductor element and the printed wiring board can be further improved.

In addition, from the viewpoint of further improving the balance of 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 the cured product was measured dynamic elastic sticky, cured to a storage elastic modulus E under the ₃₀ ℃ '30 with respect to 250 deg.] C under the storage elastic modulus E' ratio ₂₅₀ (E _'30 / E ' ₂₅₀ ) is preferably 1.05 or more and 1.75 or less.

In the cured product, if E' ₃₀ /E' ₂₅₀ satisfies the above range, the change in the elastic modulus of the printed wiring board with respect to the temperature change can be further suppressed. Thereby, even if a large temperature change occurs, deformation of the insulating layer or the like is less likely to occur, and positional displacement 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.

In order to achieve such a storage elastic modulus E' ₃₀ or E' ₃₀ /E' ₂₅₀ , it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituents of the resin composition (P), respectively. The type or amount of the compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material (E), the fiber base material, the curing accelerator, and the like, the method for producing the prepreg, and the like.

From the viewpoint of further improving the fine wiring processability of the cured product of the prepreg or the resin substrate, the prepreg preferably satisfies the following conditions. That is, the mass after drying the cured product at 120 ° C for 1 hour is referred to as the first mass, and the cured product is treated under the following conditions, and the cured product is dried at 120 ° C for 1 hour. In the case of 2 masses, the amount of film reduction defined by [{(first mass) - (second mass)} / (area of the back surface of the cured product)] × 100 is preferably 1.2 g/m ² or less. .

<condition>

The hardened product was hardened in a 3 g/L aqueous sodium hydroxide solution (solvent: diethylene glycol monobutyl ether 11.1% by volume, ethylene glycol 3.6% by volume, and pure water 85.3 vol%) at 60 ° C for 5 minutes. Swelling. Next, the swelled cured product was immersed in a roughening treatment aqueous solution (sodium permanganate 60 g/L, sodium hydroxide 45 g/L) at 80 ° C for 5 minutes to roughen the cured product. Next, the roughened cured product was immersed in a neutralizing liquid (98% by mass of sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, and pure water of 94.2% by volume) at 40 ° C for 5 minutes, thereby neutralizing the cured product.

When the amount of the film to be cured of the cured product satisfies the above range, the fine wiring workability of the cured product of the prepreg or the resin substrate can be improved. In this case, the cured product or the resin substrate of the prepreg having the film-reduction amount defined by the above formula is equal to or less than the above upper limit value, and the metal layer (circuit layer) can be kept adhered even if the surface is subjected to the roughening treatment. Caused.

In order to achieve such a reduction amount, it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituent components of the resin composition (P), respectively. The type or amount of the compound (B), the inorganic filler (C), the epoxy resin (D), the low stress material (E), the fiber base material, the curing accelerator, and the like, the method for producing the prepreg, and the like.

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, a resin substrate which is particularly excellent in balance between mechanical strength and productivity and which is suitable for a thin printed wiring board can be obtained.

Fig. 1 is a cross-sectional view showing an example of a configuration of a metal-clad laminate 200 of the present embodiment. As shown in FIG. 1, the metal-clad laminate 200 is attached to the prepreg. A metal foil 105 is provided on both sides of the insulating layer 301 composed of a cured product. The metal-clad laminate 200 can be used to form an insulating layer of a printed wiring substrate. Further, in FIG. 1, the metal foil 105 is provided on both surfaces of the insulating layer 301. However, the metal-clad laminate 200 of the present embodiment may have a structure in which the metal foil 105 is provided on a single surface of the insulating layer 301. Further, the insulating layer 301 may be formed of a cured product of a laminate in which a plurality of sheets (two or more sheets) of prepregs are stacked.

The metal-clad laminate 200 preferably satisfies the following conditions from the viewpoint of further improving the insulation reliability of the obtained printed wiring board under high temperature and high humidity. In other words, the rate of change in peel strength when the metal-clad laminate 200 is stored in an environment of 135 ° C and a humidity of 85% RH for 100 hours is preferably 30% or less. Here, the peel strength change rate is represented by 100 × (P _{1 -} P ₂ ) / P ₁ . P ₁ is a peel strength between the cured product (insulating layer 301) of the prepreg before storage and the metal foil 105 as measured according to JIS C-6481:1996, and P ₂ is a cured product of the prepreg after storage ( The peel strength between the insulating layer 301) and the metal foil 105.

In the printed wiring board 200, when the peeling strength change rate satisfies the above range, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved. In this case, since the peeling strength change rate defined by the above formula is equal to or less than the above-described upper limit value, the metal-clad laminate 200 can maintain the adhesion to the metal layer (circuit layer) even when exposed to high temperature and high humidity for a long period of time. Caused.

In order to achieve such a rate of change in peel strength, it is important to appropriately control the maleimide compound (A) and benzoic acid of the constituent components of the resin composition (P), respectively. Type or amount of compound (B), inorganic filler (C), epoxy resin (D), low stress material (E), fiber base material, hardening accelerator, etc., manufacturing method of prepreg, metal-clad laminate The manufacturing method of the board 200, etc.

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

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

The method of impregnating the fiber base material with the resin composition (P) is not particularly limited, and for example, a resin composition (P) is dissolved in a solvent to prepare a resin varnish, and the fiber base material is immersed in the resin varnish. a method of applying the above resin varnish to a fibrous substrate by various coaters; a method of blowing the above resin varnish to a fibrous substrate by a sprayer; and a resin composition by a double side of the fibrous substrate P) A method in which the resin layer (P) is laminated to the fiber base material.

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

First, the metal foil 105 is placed on the upper and lower sides or on one side of the prepreg or on the outer side of the laminate in which the prepreg is overlapped by two or more sheets. Further, it is also possible to use a laminate device or a Beckler device, and simply superimpose the metal foil 105 on the upper and lower sides or the single surface on the outer side of the prepreg or the laminate in which the prepreg is overlapped by two or more sheets. status.

Next, a laminate covering the prepreg (or a laminate of two or more prepregs) and the metal foil 105 is subjected to heat and pressure molding to obtain a metal-clad laminate 200. Here, in the case of heat press molding, it is preferred to continue pressurization until the end of cooling.

The heating temperature at the time of the heat press molding is preferably 120 ° C or more and 250 ° C or less, more preferably 150 ° C or more and 240 ° C or less.

Further, the pressure at the time of the heat press molding is preferably 0.5 MPa or more and 5 MPa. Hereinafter, it is more preferably 2.5 MPa or more and 5 MPa or less.

Further, after heat and pressure molding, post-hardening may be performed in a thermostatic chamber or the like as necessary. The post-hardening temperature is preferably 150 ° C or more and 300 ° C or less, more preferably 250 ° C or more and 300 ° C or less.

Moreover, a printed wiring board can be obtained by using this metal to cover the laminated board 200 or a resin substrate as a core board.

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

Examples of the metal constituting the metal foil 105 include copper, a copper alloy, aluminum, an aluminum alloy, silver, a silver alloy, gold, a gold alloy, zinc, a zinc alloy, nickel, a nickel alloy, tin, and tin. It is an alloy of Fe-Ni, such as alloy, iron, iron alloy, Kovar (trade name), 42 alloy, indium steel, super indium steel, W, Mo, and the like. Among these, as the metal constituting the metal foil 105, copper or a copper-based alloy is preferable because it is excellent in electrical conductivity and easy to form a circuit by etching. That is, the metal foil 105 is preferably a copper foil.

Further, as the metal foil 105, a metal foil with a carrier or the like can also be used.

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

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

The fiber base material is not particularly limited, and examples thereof include a glass fiber base material such as a glass woven fabric or a glass nonwoven fabric; a polyamide resin fiber, an aromatic polyamide resin fiber, and a wholly aromatic polyamide resin fiber. Polyurethane resin fiber; polyester resin fiber such as polyester resin fiber, aromatic polyester resin fiber, or wholly aromatic polyester resin fiber; and any one of polyimine resin fiber and fluororesin fiber as a main component Weaving or a synthetic fiber substrate composed of a non-woven fabric; a paper substrate mainly composed of kraft paper, kapok paper, or a mixed paper of kapok and kraft pulp; and the like. Any of these may be used. Among these, a glass fiber substrate is preferred. Thereby, a resin substrate having low water absorption, high strength, and low thermal expansion property can be obtained.

The thickness of the fiber base material is not particularly limited, but is preferably 5 μm or more and 150 μm or less, more preferably 10 μm or more and 100 μm or less, and still more preferably 12 μm or more and 90 μm or less. By using a fibrous base material having such a thickness, the operability in the production of the prepreg can be further improved.

When the thickness of the fiber base material is at most the above upper limit value, the impregnation property of the resin composition (P) in the fiber base material can be improved, and strand void occurrence or insulation reliability can be suppressed. Further, the through hole of the resin substrate or the insulating layer 301 can be easily formed by a laser such as carbonic acid gas, UV or excimer. Further, when the thickness of the fibrous base material is at least the above lower limit value, the strength of the fibrous base material or the prepreg can be increased. As a result, the operability can be improved, the production of the prepreg can be facilitated, and the warpage of the resin substrate can be suppressed.

As the glass fiber substrate, for example, a glass formed of one or more types selected from the group consisting of E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass, and quartz glass is used. Fiber substrate.

The resin composition (P) is a thermosetting resin composition for forming an insulating layer of a printed wiring board, and preferably contains a maleimide compound (A), benzo Compound (B) and inorganic filler (C).

The maleimide compound (A) preferably contains the maleimide compound (A1) represented by the following formula (1).

[Chemical 1]

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

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

The alkylene group having 1 or more and 10 or less carbon atoms in X ₁ is not particularly limited, and is preferably a linear or branched alkyl group.

Specific examples of the linear alkyl group include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an exopeptide group, a fluorene group, and a stretching group. Mercapto, trimethylene, tetramethylene, pentamethylene, hexamethylene and the like.

Further, examples of the branched alkyl group include, for example, -C(CH ₃ ) ₂ -(isopropylidene), -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -like alkylmethylene; -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 - such as an alkyl group and the like.

Further, the carbon number of the alkylene group in X ₁ may be 1 or more and 10 or less, 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 ethyl group, a propyl group, and an isopropyl group.

Further, R _{1 is} independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and preferably a hydrocarbon group having 1 or 2 carbon atoms, specifically, a methyl group or an ethyl group.

Further, 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. Further, b is an integer of 0 or more and 3 or less, preferably 0 or 1, more preferably 0.

Further, n ₁ is an integer of 0 or more and 10 or less, preferably an integer of 0 or more and 6 or less, more preferably an integer of 0 or more and 4 or less, and particularly preferably an integer of 0 or more and 3 or less. Further, the maleimide compound (A) preferably contains at least a compound wherein n ₁ is 1 or more in the above formula (1). Thereby, the insulating layer obtained from the resin composition (P) exhibits superior heat resistance.

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

The hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms may be a hydrocarbon group composed only of an aromatic ring, or may have a hydrocarbon group other than the aromatic ring. Y may have one or more aromatic groups, and in the case of two or more, these aromatic rings may be the same or different. Further, the aromatic ring may be either a monocyclic structure or a polycyclic structure.

Specifically, as the carbon number having an aromatic ring of 6 or more and 30 The hydrocarbon group may be, for example, a core of an aromatic compound such as benzene, biphenyl, naphthalene, anthracene, anthracene, phenanthrene, indacene, diphenyl, anthracene or anthracene. a divalent group of two hydrogen atoms.

Further, these aromatic hydrocarbon groups may have a substituent. Here, the term "aromatic hydrocarbon group" has a substituent, and means that part or all of the hydrogen atom constituting the aromatic hydrocarbon group is substituted with a substituent. As a substituent, an alkyl group is mentioned, for example.

The alkyl group as such a substituent is preferably a chain alkyl group. Further, the carbon number is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and a second butyl group.

Such a group Y preferably has a group in which two hydrogen atoms are removed from benzene or naphthalene, and is a group represented by the above formula (1a), and is preferably any one of the following formulas (1a-1) and (1a-2). The base shown by one. Thereby, the insulating layer obtained from the resin composition (P) exhibits superior heat resistance.

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

Further, in the group represented by the above formula (1a), n ₂ may be an integer of 0 or more, 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.

From the above, the cis formula (1) acyl maleic imide compound (A1) based X ₁ is preferably a carbon number of 1 or more and 3 or less linear or branched chain alkylene group, 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. Further, X ₁ is preferably a group represented by any one of the above formulas (1a-1) and (1a-2), and e is 0. Thereby, the insulating layer obtained from the resin composition (P) exhibits superior low heat shrinkability and chemical resistance.

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

Further, the maleimide compound (A) may further contain a maleimide compound (A2) of a different type from the maleimide compound (A1) represented by the above formula (1). .

As such a maleimide compound (A2), for example, 1,6'-bis-s-butyleneimine-(2,2,4-trimethyl)hexane, hexamethylene group Diamine bis-butenylene diimine, N,N'-1,2-extended ethylbis-s-butylene diimide, N,N'-1,3-propenylbis-s-butylene diimide, N,N'-1,4 An aliphatic bis-n-butylene iminoimide compound such as tetramethylenebis-synylenediamine or the like; Among these, it is particularly preferred that it is 1,6'-bis-synylenediamine-(2,2,4-trimethyl)hexane or quinoneimine-expanded bis-s-butyleneimine. The maleimide compound (A2) may be used singly or in combination of two or more.

The bis-iminyl diiminimide compound represented by the following formula (a1) and the bis-cis-butane derivative represented by the following formula (a2) are mentioned. The imine compound, the bis-cis-butadiene imine compound (A) represented by the following formula (a3), and the like. Specific examples of the bis-cis-butadiene imine compound represented by the formula (a1) include BMI-1500 (manufactured by Designer Molecules, molecular weight 1500). Specific examples of the bis-cis-butadiene imine compound represented by the formula (a2) include BMI-1700 (manufactured by Designer Molecules, molecular weight: 1700), BMI-1400 (manufactured by Designer Molecules, molecular weight: 1400), and the like. . Specific examples of the bis-cis-butadiene imine compound represented by the formula (a3) include BMI-3000 (manufactured by Designer Molecules, molecular weight 3000).

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

[Chemical 6]

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

In the above 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, and the total solid content (that is, the component other than the solvent) of the resin composition (P) is set. When it is 100% by mass, it is preferably 1.0% by mass or more and 25.0% by mass or less, more preferably 2.0% by mass or more and 22.0% by mass or less, still more preferably 5.0% by mass or more and 20.0% by mass or less. When the content of the maleimide compound (A) is within the above range, the balance between the low heat shrinkability and the chemical resistance of the cured product or the resin substrate of the obtained prepreg can be further improved.

The content of the maleimide compound (A1) contained in the maleimide compound (A) is not particularly limited, and the content of the resin contained in the resin composition (P) is not limited. When the enediminoimine compound (A) is 100% by mass, it is preferably 30.0% by mass or more and 100.0% by mass or less, more preferably 50.0% by mass or more and 100.0% by mass or less. When the content of the maleimide compound (A1) is within the above range, the balance between the low heat shrinkability and the chemical resistance of the cured product or the resin substrate of the obtained prepreg 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 Mw is at least the above lower limit value, the viscosity of the prepreg can be suppressed. Further, the upper limit of Mw is not particularly limited, but is preferably 4,000 or less, more preferably 2,500 or less. When Mw is less than or equal to the above upper limit, the impregnation of the fibrous base material is improved at the time of preparation of the resin substrate, and a more uniform resin substrate can be obtained. The Mw of the maleimide compound (A1) can be determined, for example, by GPC (gel permeation chromatography, standard material: polystyrene conversion).

Benzo Compound (B) has benzo a compound of the ring. Benzo The compound (B) may, for example, be one or more selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3).

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

[Chemistry 9]

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

Examples of X ₂ and X ₃ in the above formula (2) and the above formula (3) include the same groups as those described for X _{1 of} the above formula (1). Further, R ₂ and R ₃ in the above formula (2) and the above formula (3) can be the same as those described for R _{1 of} the above formula (1), and further, the above formula (2) and the above formula ( 3) c and d can be set to be the same as those described in a of the above formula (1).

As such a benzo In the compound (B), the compound represented by the above formula (2) and the compound represented by the above formula (3), a compound represented by the above formula (2) is preferred. Thereby, the insulating layer obtained from the resin composition (P) exhibits superior low heat shrinkability and chemical resistance.

Further, the compound represented by the above formula (2) is preferably a linear or branched chain alkyl group in which X ₂ is a carbon number of 1 or more and 3 or less, and R ₂ is a hydrocarbon group having 1 or 2 carbon atoms. c is an integer of 0 or more and 2 or less. Further, it is preferable that X ₂ is a group represented by any one of the above formulas (1a-1) and (1a-2), and c is 0. Thereby, the insulating layer obtained from the resin composition (P) exhibits superior low heat shrinkability and chemical resistance.

Benzo A preferred embodiment of the compound (B) is, for example, a compound selected from the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3). One or two or more compounds 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).

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

[11]

Benzoin contained in the resin composition (P) The content of the compound (B) is not particularly limited, and when the total solid content of the resin composition (P) (that is, the component other than the solvent) is 100% by mass, it is preferably 1.0% by mass or more and 25.0% by mass. Hereinafter, it is more preferably 2.0% by mass or more and 15.0% by mass or less. Benzo When the content of the compound (B) is within the above range, the cured product of the obtained prepreg or the resin substrate can be further improved in heat shrinkability and chemical resistance.

The content of the maleimide compound (A) contained in the resin composition (P) is relative to the maleimide compound (A) and benzo The total amount of the compound (B) is 100% by mass, preferably 35% by mass or more and 80% by mass or less. Thereby, the heat resistance, low heat shrinkability, and chemical resistance of the cured product of the obtained prepreg or the resin substrate can be further improved.

The resin composition (P) of the present embodiment may further contain an epoxy resin (D).

Examples of the epoxy resin (D) include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol E epoxy resin, bisphenol S epoxy resin, and bisphenol M epoxy resin. (4,4'-(1,3-phenylenediisopropylidene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylene) Bisphenol type epoxy resin such as diisopropyl bisphenol type epoxy resin, bisphenol Z type epoxy resin (4,4'-cyclohexadiene bisphenol type epoxy resin); phenol novolak resin Type epoxy resin, cresol novolak resin type epoxy resin, tetraphenol ethane type novolac resin type epoxy resin, novolac resin type epoxy resin having a condensed ring aromatic hydrocarbon structure, etc. Epoxy resin; biphenyl type epoxy resin; aralkyl type epoxy resin such as fluorene type epoxy resin, biphenyl aralkyl type epoxy resin; naphthalene ether type epoxy resin, naphthol type epoxy resin , a naphthalene glycol type epoxy resin, a bifunctional to tetrafunctional epoxy type naphthalene resin, a naphthyl epoxy resin, a naphthalene aralkyl type epoxy resin, or the like; a fluorene type epoxy resin; Phenoxy epoxy resin Dicyclopentadiene-type epoxy resins; epoxy resins falling primary alkenyl; adamantane type epoxy resins; fluorene type epoxy resins and the like.

As the epoxy resin (D), one of these may be used alone or two or more kinds may be used in combination, or one or two or more kinds of the prepolymers may be used in combination.

In the epoxy resin (D), from the viewpoint of further improving heat resistance and insulation reliability of the obtained printed wiring board, it is preferably selected from a bisphenol type epoxy resin, a novolak type epoxy resin, and a biphenyl type ring. One or more selected from the group consisting of an oxygen resin, an aralkyl type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, and a dicyclopentadiene type epoxy resin, more preferably selected from an aralkyl group One or more of a group consisting of a type epoxy resin, a novolak type epoxy resin having a condensed ring aromatic hydrocarbon structure, and a naphthalene type epoxy resin.

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" manufactured by Mitsubishi Chemical Corporation and "EPICLON 830S" manufactured by DIC Corporation can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", and "HP4032SS" manufactured by DIC Corporation can be used. 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 Nippon Steel Chemical Co., Ltd., "NC7000L" manufactured by Nippon Kayaku Co., Ltd., or the like can be used. As the aralkyl type epoxy resin, Nippon Chemical Co., Ltd., "NC3000", "NC3000H", "NC3000L", "NC3000S", "NC3000S-H", "NC3100", and Nippon Steel Chemical Co., Ltd. can be used. "ESN-170" and "ESN-480". As the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation can be used. As the oxime type epoxy resin, "YX8800" manufactured by Mitsubishi Chemical Corporation or the like can be used. As the naphthalene ether type epoxy resin, "HP6000", "EXA-7310", "EXA-7311", "EXA-7311L", and "EXA7311-G3" manufactured by DIC Corporation can be used.

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

Among these epoxy resins (D), an aralkyl type epoxy resin is particularly preferred. Thereby, the moisture absorption 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, and particularly preferably 800 or more. When Mw is at least the above lower limit value, the viscosity of the prepreg can be suppressed. The upper limit of Mw is not particularly limited, but is preferably 20,000 or less, more preferably 15,000 or less. When Mw is at most the above upper limit value, the impregnation property to the fiber base material is improved at the time of preparation of the prepreg, and a more uniform prepreg can be obtained. The Mw of the epoxy resin can be measured by, for example, GPC.

The content of the epoxy resin (D) contained in the resin composition (P) can be appropriately adjusted depending on the purpose, and is not particularly limited. In addition, when the total amount of the components other than the inorganic filler (C) in the resin composition (P) is 100% by mass, it is preferably 1% by mass or more and 50% by mass or less. When the content of the epoxy resin (D) is at least the above lower limit value, workability is improved and a prepreg is easily formed. When the content of the epoxy resin (D) is at most the above upper limit value, the strength or flame retardancy of the obtained printed wiring board is improved, or the linear expansion coefficient of the printed wiring board is lowered, and the effect of reducing the warpage is improved.

The resin composition (P) of the present embodiment preferably contains an inorganic filler (C). Thereby, the storage elastic modulus E' of the cured product of the obtained prepreg or the resin substrate can be improved. Further, the linear expansion coefficient of the obtained insulating layer 301 can be reduced.

Examples of the inorganic filler (C) include talc, calcined clay, uncalcined clay, mica, glass, and the like; titanium oxide, alumina, diaspore, cerium oxide, molten cerium oxide, and the like. Oxide; carbonate of calcium carbonate, magnesium carbonate, hydrotalcite, etc.; hydroxide of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc.; sulfate or sulfurous acid of barium sulfate, calcium sulfate, calcium sulfite, etc. Salt; borate of zinc borate, barium borate, barium borate, calcium borate, sodium borate, etc.; aluminum nitride, boron nitride, tantalum nitride, nitrogen A nitride such as carbon; a titanate such as barium titanate or barium titanate.

Among these, talc, alumina, glass, cerium oxide, mica, diaspore, aluminum hydroxide, magnesium hydroxide, and particularly preferably cerium oxide are preferable. As the inorganic filler (C), one of these may be used alone or two or more kinds may be used in combination.

The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 0.01 μm or more, and more preferably 0.05 μm or more. When the average particle diameter of the inorganic filler (C) is at least the above lower limit value, the viscosity of the varnish can be prevented from being excessively high, and the workability in the production of the prepreg can be improved. Further, the average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, still more preferably 1.0 μm or less. When the average particle diameter of the inorganic filler (C) is at most the above upper limit value, a phenomenon such as sedimentation of the inorganic filler (C) can be suppressed, and a more uniform resin layer can be obtained. Moreover, when the circuit size L/S (line and space) of the printed wiring board is less than 20/20 μm, it is possible to suppress the influence on the insulation between the wirings. The average particle diameter of the inorganic filler (C) is determined by, for example, a laser diffraction type particle size distribution measuring apparatus (LA-500, manufactured by HORIBA Co., Ltd.), and the particle size distribution of the particles is measured on a volume basis, and the diameter (D ₅₀ ) is taken as The average particle size.

Further, the inorganic filler (C) is not particularly limited, and an inorganic filler having an average particle diameter of monodisperse may be used, or an inorganic filler having an average particle diameter of polydisperse may be used. Further, one or a mixture of two or more kinds of inorganic fillers having an average particle diameter of monodisperse and/or polydispersity may be used in combination.

The inorganic filler (C) is preferably cerium oxide particles, preferably cerium oxide particles having an average particle diameter of 5.0 μm or less, more preferably cerium oxide particles having an average particle diameter of 0.1 μm or more and 4.0 μm or less. It is a cerium oxide particle of 0.2 μm or more and 2.0 μm or less. Thereby, the filling property of the inorganic filler (C) with respect to the fiber base material can be further improved.

The content of the inorganic filler (C) contained in the resin composition (P) is not particularly When the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, it is preferably 50.0% by mass or more and 85.0% by mass or less, and more preferably 60.0% by mass or more. And 80.0% by mass or less. When the content of the inorganic filler (C) is within the above range, the cured product or the resin substrate of the obtained prepreg can be further thermally expanded and absorbed low.

The resin composition (P) preferably further contains a low stress material (E). Thereby, the stress of the cured product of the obtained prepreg or the resin substrate can be relaxed, or the adhesion between the obtained member and other members such as the circuit layer can be further improved.

The low stress material (E) may, for example, be selected from a (meth)acrylic block copolymer; a polyfluorene oxide; an acrylonitrile modified by a carboxyl group, an amine group, a vinyl acrylate group or an epoxy group. ‧ one or more selected from butadiene rubber; aliphatic epoxy resin; and rubber particles.

The (meth)acrylic block copolymerization system contains a (meth)acrylic monomer as a block copolymer of an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, tributyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, and A. (meth)acrylic acid alkyl esters such as n-butyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate; (meth) acrylate having an alicyclic structure such as ester or cyclohexyl methacrylate; (meth) acrylate having an aromatic ring such as benzyl methacrylate; 2-trifluoroethyl methacrylate; a (fluoro)alkyl ester of (meth)acrylic acid; a carboxyl group-containing acrylic monomer having a carboxyl group in a molecule of acrylic acid, methacrylic acid, maleic acid, maleic anhydride or the like; 2-hydroxyethyl acrylate Ester, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacryl 4-hydroxybutyl acrylate, mono(meth) acrylate of glycerol, etc., hydroxyl group-containing acrylic monomer having a hydroxyl group in the molecule; glycidyl methacrylate, methyl glycidyl methacrylate, methyl 3,4-epoxycyclohexylmethyl acrylate, etc., an acrylic monomer having an epoxy group in the molecule; allyl acrylate, allyl methacrylate, etc., having an allyl group-containing allylic group in the molecule Acrylic acid-containing monomer; γ-methyl propylene methoxy propyl trimethoxy decane, γ-methyl propylene methoxy propyl triethoxy decane, etc. Monomer; ultraviolet-absorbing acrylic monomer having a benzotriazole-based ultraviolet absorbing group such as 2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole Wait.

Further, in the above (meth)acrylic block copolymer, a monomer other than the above acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include an aromatic vinyl compound such as styrene or α-methylstyrene, a conjugated diene such as butadiene or isoprene, ethylene or propylene. An olefin such as isobutylene.

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

In particular, the (meth)acrylic block copolymer is preferably a polymer block having a low glass transition temperature (Tg) from the viewpoint of improving heat resistance, light resistance, and crack resistance. (S) (soft block), a block copolymer having a polymer block (H) (hard block) having a higher Tg than the polymer block (S), more preferably having a polymerization in the middle The bulk block (S), a triblock copolymer having an HSH structure of a polymer block (H) at both ends.

A preferred example of the (meth)acrylic block copolymer in the resin composition (P) is that the polymer block (S) is composed of butyl acrylate (BA) as a main monomer. The polymer and the polymer block (H) are a polymer composed of methyl methacrylate (MMA) as a main monomer, that is, a polymethyl methacrylate block-polybutyl acrylate block- Polymethyl methacrylate terpolymer (PMMA-b-PBA-b-PMMA) or the like.

In addition, as the (meth)acrylic block copolymer, for example, "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", and "Nanostrength M53" (Arkema company, Commercial products such as PMMA-b-PBA-b-PMMA), trade name "Nanostrength E21", "Nanostrength E41" (made by Arkema Co., Ltd., PSt (polystyrene)-b-PBA-b-PMMA).

Examples of the polyoxymethane compound include polyoxyxylene rubber, polyoxygenated oil, polyfluorene oxide powder, polyoxynoxy resin, polyoxynoxy epoxy resin, amine modified polyoxynoxy resin, epoxy group-containing and benzene. A 3-dimensional crosslinked polyoxyxylene resin or the like.

The aliphatic epoxy resin is preferably an aliphatic epoxy resin having no cyclic structure other than the epoxy propyl group, and more preferably a bifunctional or higher aliphatic epoxy resin having two or more epoxy propyl groups. Since such an epoxy resin is not easily oxidized by an epoxy group, it is less likely to cause an increase in the elastic modulus due to the heat history.

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

The core-shell type rubber particles are rubber particles having a core layer and a shell layer, For example, the shell layer of the outer layer is composed of a glassy polymer, the core layer of the inner layer is composed of a rubbery polymer, or the shell layer of the outer layer is composed of a glassy polymer, and the intermediate layer is composed of a rubbery polymer. A three-layer structure particle composed of a glassy polymer and a core layer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3822, AC3816N (trade name, manufactured by GANTSU Chemical Co., Ltd.), and METABLEN KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, 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 acryl rubber particles include METABLEN W300A (average particle diameter: 0.1 μm) and W450A (average particle diameter: 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

The polysiloxane particles are not particularly limited as long as they are rubber elastic fine particles formed of an organopolysiloxane, and may be, for example, fine particles composed of a polyoxyxylene rubber (organic polyoxyalkylene crosslinked elastomer), and A core-shell structured particle coated with a polyfluorinated oxygen of a three-dimensional crosslinked type main body in a core portion of a cross-linked main body. As the polyoxyxene rubber microparticles, KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), TORAYFIL E-500, TORAYFIL E-600 (manufactured by Toray Dow Corning Co., Ltd.) can be used. Sale.

The content of the low-stress material (E) contained in the resin composition (P) is not particularly limited, and when the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass It is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 1.0% by mass or more and 8.0% by mass or less. If the content of the low stress material (E) is the above range The stress of the cured product or the resin substrate of the obtained prepreg can be more moderated, or the adhesion between the cured member and the other members such as the circuit layer can be further improved.

Further, a curing accelerator or a coupling agent may be appropriately blended in the resin composition (P) as needed.

The curing accelerator is not particularly limited, and examples thereof include a phosphine compound, a compound having a phosphonium salt, and an imidazole compound. One type or a combination of two or more types may be used. Among these, an imidazole compound is preferred. Since the imidazole compound is a compound having a particularly superior catalytic function, the maleimide compound (A) and the benzoic acid can be more reliably promoted. Polymerization of compound (B).

The imidazole-based compound is not particularly limited, and examples thereof include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, and 2-dodecyl group. Imidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1 -Cyanomethyl-2-methyl-imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano Ethyl-2-phenylimidazole or the like may be used alone or in combination of two or more. Among these, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 2-ethyl-4-methylimidazole are preferred. By using these compounds, the maleimide compound (A) and benzo can be further promoted. The reaction of the compound (B) enhances the formability and at the same time, the heat resistance of the obtained cured product can be obtained.

The phosphine compound may, for example, be a phosphine such as an ethyl phosphine, an alkylphosphine such as a propylphosphine or a phenylphosphine; a dimethylphosphine, a dialkylphosphine such as diethylphosphine, or a diphenylphosphine. Grade II phosphine such as methylphenylphosphine or ethylphenylphosphine; trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine trialkylphosphine, tricyclohexylphosphine, triphenyl Phosphine Diphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tricresylphosphine, tris-styrylphosphine, ginseng (2,6-dimethoxyphenyl)phosphine, tri-4-methyl a tertiary phosphine such as phenylphosphine, tri-4-methoxyphenylphosphine or tri-2-cyanoethylphosphine. Among these, it is preferred to use a tertiary phosphine.

Further, examples of the compound having a phosphonium salt include a compound having a tetraphenylphosphonium salt, an alkyltriphenylphosphonium salt, and the like, and specific examples thereof include tetraphenylphosphonium thiocyanate and tetra-p-methylphenylboronic acid. Phenylhydrazine, butyl triphenylphosphonium thiocyanate, and the like.

The content of the hardening accelerator is relative to the maleimide compound (A) and benzo The total amount of the compound (B) is 100 parts by mass, preferably 0.01 to 5.0 parts by mass, more preferably 0.05 to 3.0 parts by mass, particularly preferably 0.1 to 1.5 parts by mass. By setting the content of the hardening accelerator to such a range, the heat resistance of the cured product obtained from the resin composition (P) can be further improved.

Further, the resin composition (P) may also contain a coupling agent. The coupling agent may be directly added during the preparation of the resin composition (P), and when the resin composition (P) contains the inorganic filler (C), it may be added to the inorganic filler (C) in advance. By the use of a coupling agent, the wettability of the interface between the fibrous base material or the inorganic filler (C) and each resin can be improved. Therefore, it is preferred to use a coupling agent to improve the heat resistance of the cured product of the obtained prepreg or the resin substrate.

The coupling agent may, for example, be a decane coupling agent such as an epoxy decane coupling agent, a cationic decane coupling agent or an amino decane coupling agent, a titanate coupling agent or a polyasoxy oil type coupling agent. The coupling agent may be used alone or in combination of two or more.

Thereby, the wettability of the interface between the fiber base material or the inorganic filler (C) and each resin can be improved, and the heat resistance of the cured product of the obtained prepreg or the resin substrate can be further improved.

As the decane coupling agent, various compounds can be used, and examples thereof include epoxy decane, amino decane, alkyl decane, urea decane, decyl decane, and vinyl decane.

Specific examples of the compound include γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, and N-β(aminoethyl)γ-aminopropyltrimethoxydecane. , N-β (aminoethyl) γ-aminopropyl methyl dimethoxy decane, N-phenyl γ-aminopropyl triethoxy decane, N-phenyl γ-aminopropyl Trimethoxydecane, N-β(aminoethyl)γ-aminopropyltriethoxydecane, N-6-(aminohexyl)3-aminopropyltrimethoxydecane, N-(3 -(trimethoxymercaptopropyl)-1,3-benzenedimethane, γ-glycidoxypropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, γ- Glycidoxypropylmethyldimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, methyltrimethoxydecane And γ-ureidopropyl triethoxy decane, vinyl triethoxy decane, etc., one or a combination of two or more of them. Among them, epoxy decane or decyl decane is preferable. The amino decane, as the amino decane, is more preferably a grade 1 amino decane or an anilino decane.

The amount of the coupling agent to be added is appropriately adjusted in accordance with the specific surface area of the inorganic filler (C), and is not particularly limited. The total solid content of the resin composition (P) (that is, the component other than the solvent) is set to 100% by mass. In time, it is preferably 0.01% by mass or more and 1% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less.

When the content of the coupling agent is at least the above lower limit value, the inorganic filler (C) can be sufficiently coated, and the heat resistance of the cured product or the resin substrate of the obtained prepreg can be improved. In addition, when the content of the coupling agent is at most the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress a decrease in the bending strength or the like of the cured product of the obtained prepreg or the resin substrate.

Further, in the resin composition (P), a pigment, a dye, an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, and a hardening may be added within a range not impairing the object of the present invention. Additives other than the above components such as a fuel, an ion trapping agent, and the like.

Examples of the pigment include multi-ring pigments such as kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, yttrium yellow, chromium hydroxide, chromium oxide, cobalt aluminate, synthetic ultramarine, and the like. Azo pigments, etc.

Examples of the dye include isoindolinone, isoporphyrin, and quinoline yellow. , diketopyrrolopyrrole, hydrazine, hydrazine, hydrazine, hydrazine, , quinacridone, benzimidazolone, purpurin, indigo, methylene azo dye, and the like.

The resin composition (P) is used in various organic solvents, and is carried out by various mixers such as an ultrasonic dispersion method, a high pressure conflict dispersion method, a high-speed rotary dispersion method, a bead milling method, a high-speed shear dispersion method, and a rotation-revolving dispersion method. Dissolved, mixed, and stirred to form a resin varnish (I).

The organic solvent used for the resin varnish (I) may, for example, be acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane or cyclohexanone. , tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl hydrazine, ethylene glycol, serotonin, 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, and particularly preferably 50% by mass or more and 70% by mass or less. Thereby, the impregnation property of the resin varnish (I) with respect to the fiber base material can be further improved.

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

When the total solid content (that is, the component other than the solvent) of the resin composition (P) is 100% by mass, the ratio of the maleimide compound (A) is preferably 1.0% by mass or more. 25.0% by mass or less, benzo The ratio of the compound (B) is 1.0% by mass or more and 25.0% by mass or less, and the ratio of the inorganic filler (C) is 50.0% by mass or more and 85.0% by mass or less.

Further, the ratio of the maleimide compound (A) is more preferably 5.0% by mass or more and 20.0% by mass or less, and benzo The ratio of the compound (B) is 2.0% by mass or more and 15.0% by mass or less, and the ratio of the inorganic filler (C) is 60.0% by mass or more and 80.0% by mass or less.

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

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

As shown in FIG. 2, the printed wiring board 300 of the present embodiment may be a single-sided printed wiring board, or may be a double-sided printed wiring board or a multilayer printed wiring board. The double-sided printed wiring board refers to a printed wiring board in which the metal layer 303 is laminated on the double surface of the insulating layer 301. In addition, the multilayer printed wiring board refers to a metal layer 303 in which two or more layers are laminated on the insulating layer 301 via an interlayer insulating layer (also referred to as an build-up layer) by a plating through-hole method or an extension method. Printed wiring substrate.

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

In the case where the printed wiring board 300 is a multilayer printed wiring board as shown in FIG. 3, the metal layer 303 is a circuit layer in the core layer 311 or the build-up layer 317.

The metal layer 303 is formed, for example, on the surface of the metal foil 105 or the insulating layer 301 which is subjected to chemical treatment or plasma treatment, by a SAP (Semi-Addition Process) method. in After the electroless metal plating film 308 is applied to the metal foil 105 or the insulating layer 301, the non-circuit forming portion is protected by a plating resist, and the electrolytic metal plating layer 309 is applied by electroplating. Thereafter, the plating resist is removed and the electroless metal plating film 308 is removed by rapid etching, whereby the metal layer 303 is formed on the metal foil 105 or the insulating layer 301.

The circuit size of the metal layer 303 can be 25 μm / 25 μm or less, and particularly 15 μm / 15 μm or less, in terms of line and space (L/S). In general, when the circuit size is reduced and fine wiring is formed, the insulation reliability between wirings is lowered. However, the printed wiring board 300 of the present embodiment can be made into a fine wiring having a line pitch (L/S) of 15 μm/15 μm or less, and can be made finer than a line pitch (L/S) of 10 μm/10 μm or less.

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

The insulating layer 305 in the build-up layer 317 is not particularly limited as long as it is made of an insulating material, and may be composed of, for example, a resin film or a prepreg. Among these, the prepreg is a sheet-like material, and has various characteristics such as dielectric properties, mechanical properties under high temperature and high humidity, and electrical connection reliability, and is suitable for the manufacture of the build-up layer 317 of the printed wiring board. good.

As the prepreg, the above prepreg is particularly preferred.

The thickness of the insulating layer 301 in the core layer 311 (including the insulating layer 301 in the printed wiring board 300 not including the build-up layer 317) 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 between mechanical strength and productivity, and is suitable for the insulating layer 301 of a thin printed wiring board.

The thickness of the insulating layer 305 in the build-up layer 317 is preferably 0.015 mm. Above and 0.05mm or less. When the thickness of the insulating layer 305 is within the above range, the insulating layer 305 is particularly excellent in balance between mechanical strength and productivity, and is suitable for the insulating layer 305 of a thin printed wiring board.

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

First, a metal-clad laminate 200 is prepared.

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

Next, a via hole 307 is formed in the insulating layer 301. The through hole 307 can be formed, for example, using a drill or laser irradiation. Lasers for laser irradiation include, for example, excimer lasers, UV lasers, carbon dioxide lasers, and the like. The resin residue or the like after the formation of the through hole 307 may be removed by an oxidizing agent such as permanganate or dichromate.

Further, the through hole 307 may be formed in the insulating layer 301 before the metal foil 105 is removed by an etching process.

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

The chemical liquid treatment is not particularly limited, and examples thereof include a method of using an oxidizing agent solution having an organic decomposition action, and the like. Further, as the plasma treatment, for example, a method in which an active species (plasma, radical, or the like) having a strong oxidation effect is directly applied to an object to remove an organic residue can be mentioned.

Next, a metal layer 303 is formed. Metal layer 303 can be formed, for example, by a semi-additive process (SAP) or a modified semi-additive process (MSAP). The details are as follows.

First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 or the through hole 307 by using an electroless plating method to achieve a printing cloth. The two sides of the wire substrate 300 are electrically connected. Further, the through hole 307 can be appropriately buried by a conductor paste or a resin paste. Next, an example of the electroless plating method will be described. For example, first, a catalyst core is provided on the surface of the metal foil 105 or the insulating layer 301 or in the through hole 307. The catalyst core is not particularly limited, and for example, a noble metal ion or a palladium colloid can be used. Next, the electroless metal plating film 308 is formed by electroless plating treatment using the catalyst core as a core. For the electroless plating treatment, for example, a solution containing copper sulfate, formaldehyde, a neutralizing agent, sodium hydroxide or the like can be used. Further, after the electroless plating, it is preferred to carry out heat treatment at 100 to 250 ° C to stabilize the plating film. From the viewpoint of forming a film capable of suppressing oxidation, it is particularly preferably a heat treatment at 120 ° C to 180 ° C. Further, the average thickness of the electroless metal plating film 308 is, for example, about 0.1 to 2 μm.

Next, 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 a liquid or dry film can be used. In the case of forming a fine wiring, it is preferable to use a photosensitive dry film as a plating resist. An example of using a photosensitive dry film will be described below. For example, a photosensitive dry film is laminated on the electroless metal plating film 308, and the non-circuit forming region is exposed to light hardening, and the unexposed portion is dissolved and removed by the developing solution. The plating resist is formed by leaving the cured photosensitive dry film.

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

Next, the plating resist is removed using an alkaline stripper or sulfuric acid or a commercially available resist stripper or the like.

Next, 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 (rapid etching) or the like. Here, the soft etching treatment can be performed by etching using an etching solution containing sulfuric acid and hydrogen peroxide. Thereby, the metal layer 303 can be formed. The metal layer 303 is composed of a metal foil 105 and/or an electroless metal plating film 308 and an electrolytic metal plating layer 309.

Further, on the printed wiring board 300, the build-up layer 317 may be laminated as needed, and a plurality of layers may be formed by repeating the steps of interlayer connection and circuit formation by a half-addition process.

As described above, the printed wiring board 300 of the present embodiment can be obtained.

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

First, the printed wiring board 300 obtained by the above method is prepared. Next, on the metal layer 303 (circuit layer) of the printed wiring board 300, an additional layer is laminated as needed, and the step of indirectly connecting the layers and forming the circuit by repeating the semi-additive method is repeated. Then, the solder resist layer 401 is laminated on both sides or one side of the printed wiring board 300 as needed.

The method for forming the solder resist layer 401 is not particularly limited, and examples thereof include a method of laminating a dry film type solder resist, a method of forming by exposure and development, or borrowing A method in which a liquid resist is patterned, and a pattern is formed by exposure and development.

Next, the semiconductor element 407 is placed on the connection terminal belonging to a part of the circuit layer of the printed wiring board 300 via the solder bump 410. Next, a reflow process is performed, whereby the semiconductor element 407 is fixed to the connection terminal via the solder bump 410. Thereafter, the semiconductor element 407, the solder bump 410, and the like are sealed with a sealing material 413, whereby the semiconductor device 400 as shown in FIGS. 4 and 5 is obtained.

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

Further, in the above-described embodiment, the circuit layers 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 circuit layer of the semiconductor element 407 and the printed wiring substrate 300 may be connected by a bonding wire.

[Examples]

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited thereto. Further, in the examples, "parts" means "parts by mass" unless otherwise specified. Further, each thickness is represented by an average film thickness.

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

Maleimide compound 1: In the formula (1), n ₁ is 0 or more and 3 or less, X ₁ is a group represented by "-CH ₂ -", and a is 0, and b is a compound of 0 (BMI) -2300, manufactured by Daiwa Chemical Industrial Co., Ltd., Mw=750)

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

Maleimide compound 3: 4,4'-diphenylmethane maleimide (in the formula (1), n ₁ is 0, and X ₁ is "-CH ₂ -" Base, a compound with a 0 and b being 0, BMI-1000, manufactured by Daiwa Kasei Co., Ltd.)

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

Maleimide compound 5: stilbene-expanded maleimide (BMI-1500, a maleimide compound represented by formula (a1), manufactured by Designer Molecules, having a molecular weight of 1,500 )

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

Benzo Compound 1: Benzene represented by formula (2-1) Compound (Pd type benzophenone) , Shikoku Chemical Industry Co., Ltd.)

Benzo Compound 2: Benzene represented by formula (3-1) Compound (Fa type benzophenone) , Shikoku Chemical Industry Co., Ltd.)

Epoxy resin 1: aralkyl 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 Glycol Epoxy Resin (EPICLON HP-4032D, manufactured by DIC Corporation)

Epoxy Resin 4: sesquioxane type epoxy resin (COMPOCERAN SQ502-8, manufactured by Arakawa Chemical Industries, Ltd.)

Phenol Resin 1: Novolak-type phenol resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)

Inorganic filler 1: cerium oxide (SC4050, manufactured by Admatech Co., Ltd., average particle diameter: 1.1 μm, phenylamino decane-treated cerium oxide slurry)

Low stress material 1: carboxylic acid terminal acrylonitrile ‧ butadiene rubber (manufactured by PTI JAPAN, CTBN1008SP)

Low stress material 2: Amino terminal acrylonitrile ‧ butadiene rubber (ATBN1300X16, manufactured by PTI JAPAN)

Low stress material 3: polyxanthene oxide (3-dimensional cross-linked polyoxyl resin containing epoxy group and phenyl group, manufactured by Toray Dow Corning Co., Ltd., AY42-119)

Low stress material 4: Polyoxyl oxide (polyoxyl epoxy resin, manufactured by Toray Dow Corning, BY16-115)

Low stress material 5: polyfluorene oxide (modified polyoxyl resin with amine group at both ends of the molecular chain, manufactured by Toray Dow Corning, BY16-853)

Low stress material 6: Acrylic block copolymer (block copolymer of acrylic monomer (PMMA-b-PBA-b-PMMA, b=block), number average molecular weight: about 10,000, manufactured by Arkema, Nanostrength M51)

Hardening accelerator 1: 2-phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW)

Hardening accelerator 2: tetraphenylphosphonium tetrap-tolylborate (made by Behind Chemical Industry Co., Ltd., TPP-MK)

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

[1]Prepreg 1 1. Modification of resin varnish 1

Each component was dissolved or dispersed according to the solid content ratio shown in Table 1, and a mixed liquid adjusted to a nonvolatile content of 70% by mass by methyl ethyl ketone was prepared. Thereafter, the mixed solution was stirred using a high-speed stirring device to prepare a resin varnish 1.

2. Manufacturing of prepreg (prepreg 1)

The glass woven fabric (cloth type #2118, T glass, basis weight 114 g/m ² ) was impregnated with the resin varnish 1 by a coating device. Thereafter, the glass woven fabric was dried by a hot air drying apparatus at 140 ° C for 10 minutes to obtain a prepreg 1 (P1) having a thickness of 107 μm.

(prepreg 2~22)

The prepreg 2 to 22 were produced in the same manner as the prepreg 1 except that the type of the resin varnish was changed as shown in Table 1. Among them, from the viewpoint of solubility, varnish 19 adjusts the solid content concentration by dimethylformamide.

(Example 1) 1. Manufacturing of resin substrate

An ultra-thin copper foil (Micro Thin Ex, 2.0 μm, manufactured by Mitsui Mining Co., Ltd.) was superposed on both sides of the prepreg 1. Then, it was subjected to heat and pressure molding at 4 MPa and 230 ° C for 2 hours to obtain a resin substrate. The thickness of the core layer (portion composed of the resin substrate) of the obtained metal foil-attached resin substrate was 0.107 mm.

2. Manufacturing of printed wiring substrates

First, the ultra-thin copper foil layer on the surface of the metal foil-attached resin substrate obtained in the above paragraph was subjected to a roughening treatment of about 1 μm. Thereafter, a carbon dioxide gas laser is used to form an interlayer connection. 80 μm through hole. Next, a resin substrate with a metal foil was placed in a container filled with a swelling solution of 60 ° C (Stowing Dip Securiganth P, manufactured by Atotech Japan Co., Ltd.), and after immersing for 5 minutes, the resin substrate with the metal foil was taken out from the container. . Then, a resin substrate with a metal foil was placed in a container filled with a potassium permanganate aqueous solution (Concentrate Compact CP, manufactured by Atotech Japan Co., Ltd.) at 80 ° C, and after immersing for 2 minutes, the mixture was neutralized and passed through the through hole. Degumming treatment. Next, the resin substrate with the metal foil after the desmear treatment was subjected to electroless copper plating to have a thickness of 0.5 μm. Next, the thickness was changed to 18 μm to form a plating resist for electrolytic copper plating, and pattern copper plating was performed. Thereafter, it was post-cured by heating at 150 ° C for 30 minutes. Next, the plating resist was peeled off and subjected to rapid etching in a comprehensive manner to form a pattern of L/S = 15/15 μm.

(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 type of the prepreg was replaced as shown in FIG. 2 .

Moreover, the following evaluation was performed about the resin substrate obtained from each Example and the comparative example. The evaluation results are shown in Table 2.

(1) Glass transition temperature

The measurement of the glass transition temperature was carried out using a dynamic viscoelasticity analyzer (DMA apparatus, manufactured by TA Instrument Co., Ltd., Q800).

First, a test piece of 8 mm × 40 mm was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed by an etching solution (iron chloride solution, 35 ° C) to obtain a cured product of the prepreg. Next, using the obtained cured product of the prepreg at a heating rate of 5 ° C / min, frequency The dynamic viscoelasticity measurement was performed at a rate of 1 Hz. Further, the glass transition temperature was set to a temperature at which the tan δ at the frequency of 1 Hz showed the maximum value.

(2) Storage elastic modulus E'

The measurement of the storage elastic modulus E' was carried out using a dynamic viscoelasticity analyzer (DMA apparatus, manufactured by TA Instrument Co., Ltd., Q800).

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

Next, the obtained cured product of the prepreg was subjected to storage elastic modulus measurement at 30° C. and 250° C. at a temperature increase rate of 5° C./min and a frequency of 1 Hz, and the storage elastic modulus E′ _{30 at} 30° C. was calculated. Storage elastic modulus E' ₂₅₀ and E' ₃₀ /E' _{250 at} 250 °C.

(3) Size shrinkage

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

Next, the obtained cured product of the prepreg was heated from 30 ° C to a temperature of 10 ° C/min, a load of 10 g, and a compression mode using a thermomechanical analyzer TMA (manufactured by TA Instrument Co., Ltd., Q400). Thermomechanical analysis of the process at 260 ° C with the process of maintaining at 260 ° C for 1 hour. Then, the maximum thermal expansion amount L ₁ from the reference length L ₀ of the prepreg cured product and the thermal expansion amount L ₂ from the reference length L _{0 at} which the prepreg cured product was held at 260 ° C for 1 hour were obtained. . Next, the dimensional shrinkage ratio represented by 100 × (L _{1 -} L ₂ ) / L _{0 was} calculated.

(4) Linear expansion coefficient

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

Next, the obtained cured product of the prepreg was subjected to a thermomechanical analyzer TMA (manufactured by TA Instrument Co., Ltd., Q400) under the conditions of a temperature range of 30 to 260 ° C, a temperature increase rate of 10 ° C/min, a load of 10 g, and a compression mode. Thermomechanical analysis (TMA) was measured for 2 cycles. The average value α ₁ of the linear expansion coefficients in the plane direction (XY direction) in the range of 50 ° C to 150 ° C and the average value α ₂ of the linear expansion coefficients in the plane direction (XY direction) in the range of 150 ° C to 250 ° C were calculated.

Further, the coefficient of expansion is the value of the second period.

(5) Film reduction

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

Next, the cured product obtained by drying the cured product of the prepreg at 120 ° C for 1 hour is referred to as the first mass, and the cured product is treated under the following conditions, and then the cured product is dried at 120 ° C for 1 hour. In the case of the second mass, the amount of film reduction defined by [{(first mass) - (second mass)} / (area sum of the front and back surfaces of the cured product)] × 100 was calculated.

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The cured product was immersed in a 3 g/L sodium hydroxide solution (solvent: diethylene glycol monobutyl ether 11.1% by volume, ethylene glycol 3.6% by volume, and pure water 85.3 vol%) at 60 ° C for 5 minutes. Thereby, the hardened material is swollen. Next, the swelled cured product was immersed in a roughening treatment aqueous solution (sodium permanganate 60 g/L, sodium hydroxide 45 g/L) at 80 ° C for 5 minutes to roughen the cured product. Next, the roughened cured product was immersed in a neutralizing liquid (98% by mass of sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, and pure water of 94.2% by volume) at 40 ° C for 5 minutes, thereby neutralizing the cured product.

(6) Dimensional change rate

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

Next, the obtained cured product of the prepreg was subjected to a temperature of 10 ° C/min, a load of 10 g, and a compression mode using a thermomechanical analyzer TMA (manufactured by TA Instrument Co., Ltd., Q400) at 10 ° C to 10 The process of heating to 300 ° C °C / min, and the thermomechanical analysis of the process of cooling from 300 ° C to 10 ° C / min to 30 ° C. Then, the longitudinal direction length of the cured product before the thermomechanical analysis was measured as the reference length L ₀ and the longitudinal direction length L ₁ of the cured product at 30 ° C during the temperature lowering process. Next, the dimensional change ratios indicated by 100 × (L _{1 -} L ₀ ) / L _{0 were} calculated from the obtained L ₀ and L ₁ .

(7) Rate of change in peel strength

The peeling strength change rate represented by 100 × (P _{1 -} P ₂ ) / P ₁ when the obtained resin substrate (metal-clad laminate) was stored in an environment of 135 ° C and a humidity of 85% RH for 100 hours 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. Further, the peel strength between the cured product of the prepreg and the metal foil measured in accordance with JIS C-6481:1996 after storage in the P ₂ system.

(8) Reliability evaluation of insulation between thin wires

On the fine circuit pattern of L/S=15/15 μm on the printed wiring board, a build-up building material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated to prepare a hardened test sample. Using this test sample, the continuous wet insulation resistance was evaluated under the conditions of 130 ° C, humidity 85%, and applied voltage 3.3 V. Further, the resistance value of 10 ⁶ Ω or less is regarded as a failure. The evaluation criteria are as follows.

○: No problem for more than 500 hours

△: 200~ under 500 hours of failure

×: There is a fault in less than 200 hours

(9) Thin line processing evaluation

The fine line processability of the printed wiring board on which the fine circuit pattern of L/S = 15/15 μm was formed by a laser microscope was evaluated by visual inspection and conduction inspection of a thin wire (circuit). The evaluation criteria are as follows.

◎: There is no problem with the shape and conduction of the thin wires.

○: There is a problem with the shape of one of the thin wires, but there is no short circuit and the wiring is broken, and there is substantially no problem.

×: There is a short circuit and the wiring is broken.

(10) Reliability evaluation of through-hole insulation

In the manufacture of the above printed wiring board, 20 pairs of layers are formed so as to be 80 μm between the walls. 80 μm through hole. Next, on the circuit pattern, a build-up building material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated to prepare a hardened test sample. Using this test sample, the insulation resistance in continuous humidity was evaluated under conditions of 130 ° C, humidity of 85%, and applied voltage of 5.5 V. Further, the resistance value of 10 ⁶ Ω or less is regarded as a failure. The evaluation criteria are as follows.

◎: no problem for more than 500 hours (good)

○: There is a fault in 200~500 hours (substantially no problem)

△: There is a fault in less than 200 hours (substantially unusable)

×: There is a fault in less than 100 hours (cannot be used)

(11) Warpage evaluation of semiconductor devices

After the circuit board having formed the circuit pattern, the printed wiring board was laminated to build a building material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) and then cured. Next, this cured product was subjected to circuit processing by a semi-additive method. On this, a semiconductor element having solder bumps of 10 mm in length × 10 mm in width × 100 μm in thickness was mounted. Next, the semiconductor element was sealed with an underfill (CRP-4160G, manufactured by Sumitomo Bakelite Co., Ltd.), and hardened at 150 ° C for 2 hours. Finally, a semiconductor device was fabricated by cutting into 15 mm × 15 mm.

The warpage at 260 ° C of the obtained semiconductor device was evaluated using a temperature-variable laser three-dimensional measuring machine (form LS220-MT100MT50, manufactured by Hitachi, Technology and Service Co., Ltd.). In the sample chamber of the above-mentioned measuring machine, a semiconductor device was placed with the semiconductor element facing downward, and the displacement in the height direction was measured, and the value at which the displacement difference was the largest was used as the amount of warpage. The evaluation criteria are as follows.

◎: The amount of warpage is less than 30μm

○: The amount of warpage is 30 μm or more and less than 50 μm.

×: The amount of warpage is 50 μm or more

(12) Thermal cycle test

First, four semiconductor devices obtained by (11) were prepared. These semiconductor devices were treated at 85 ° C and a temperature of 85% RH for 168 hours, and then treated three times in an IR reflow furnace (peak temperature: 260 ° C). Thereafter, the conditions were set to one cycle at -55 ° C (15 minutes) and 125 ° C (15 minutes) in the atmosphere, and the conditions were subjected to 500 cycles. Next, the presence or absence of abnormality of the semiconductor element and the solder bump was observed using an ultrasonic imaging device (FS300 manufactured by Hitachi Construction Machinery, Inc.).

◎: There are no abnormalities in semiconductor components and solder bumps.

○: Cracks are seen in one of the semiconductor components and/or solder bumps, but there is no problem in practical use.

×: A crack is partially or wholly seen in one or more of the semiconductor element and/or the solder bump, and there is a problem in practical use.

Claims (15)

A prepreg obtained by impregnating a fiber base material with a thermosetting resin composition, and when the cured product obtained by heat-treating the prepreg at 230 ° C for 2 hours is subjected to thermomechanical analysis, The ratio of the average linear expansion coefficient α ₂ calculated in the in-plane direction of the hardened material in the range of 150 ° C to 250 ° C with respect to the average linear expansion coefficient α ₁ calculated in the range of 50 ° C to 150 ° C (α ₂ /α) ₁ ) is 0.7 or more and 2.0 or less, and the average linear expansion coefficient α ₂ is 8.0 ppm/° C. or less. The prepreg according to claim 1, wherein the cured product obtained by heat-treating the prepreg at 230 ° C for 2 hours is subjected to a process of raising the temperature from 30 ° C to 260 ° C at 10 ° C / min, When the thermomechanical analysis is performed at 260 ° C for one hour, the length of the cured product before the thermomechanical analysis is measured is the reference length L ₀ , and the cured product is from the reference length L _{0 .} The maximum amount of thermal expansion is set to L ₁ , and the amount of thermal expansion from the reference length L ₀ when the cured product is held at 260 ° C for 1 hour is set to L ₂ , and is 100 × (L _{1 -} L _{2 ).} The dimensional shrinkage ratio shown by /L ₀ is 0.15% or less. The prepreg according to claim 1, wherein the cured product obtained by heat-treating the prepreg at 230 ° C for 2 hours is subjected to a process of raising the temperature from 30 ° C to 300 ° C at 10 ° C / min, In the thermomechanical analysis of the surface direction in the compression mode in the process of cooling from 300 ° C to 30 ° C at 10 ° C / min, the length of the cured product before the thermomechanical analysis is set as the reference length L _{0. In} the case where the longitudinal direction length of the cured product at 30 ° C in the above-described cooling process is L ₁ , the dimensional change ratio represented by 100 × (L _{1 -} L ₀ ) / L ₀ is -0.20% or more. The prepreg according to claim 1, wherein the cured product has a glass transition temperature of 260 ° C or higher when the dynamic viscoelasticity measurement is performed under conditions of a temperature increase rate of 5 ° C/min and a frequency of 1 Hz. The prepreg according to claim 1, wherein the storage elastic modulus E' ₃₀ of the cured product at 30 ° C is relative to the storage elastic modulus E at 250 ° C when the cured product is subjected to dynamic viscoelasticity measurement. The ratio of ' ₂₅₀ (E' ₃₀ /E' ₂₅₀ ) is 1.05 or more and 1.75 or less. The prepreg according to claim 1, wherein the prepreg has a thickness of 20 μm or more and 220 μm or less. The prepreg according to claim 1, wherein the thermosetting resin composition contains a maleimide compound (A) and a benzoate. Compound (B) and inorganic filler (C). The prepreg of claim 7, wherein the maleimide compound (A) comprises a maleimide compound (A1) represented by the following formula (1); (In the above formula (1), n ₁ is an integer of 0 or more and 10 or less, and each of X _{1 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the following formula (1a), and a formula a group represented by -SO ₂ -", a group represented by "-CO-", an oxygen atom or a single bond, and each of R _{1 is} independently a hydrocarbon group having 1 or more and 6 or less carbon atoms, and a is independently 0 or more and 4 The following integers, b are each independently an integer of 0 or more and 3 or less ;) (In the above formula (1a), Y is a hydrocarbon group having an aromatic ring having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 0 or more). The prepreg of claim 7, wherein the benzoate is The compound (B) includes one or more selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3); (In the above formula (2), X _{2 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the above formula (1a), a group represented by the formula "-SO ₂ -", and "-CO". -" represents a group, an oxygen atom or a single bond, and R _{2 is} independently a hydrocarbon group having 1 to 6 carbon atoms, and c is independently an integer of 0 or more and 4 or less; (In the above formula (3), X _{3 is} independently an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the above formula (1a), a group represented by the formula "-SO ₂ -", and "-CO". -" represents a group, an oxygen atom or a single bond, and 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 prepreg according to claim 7, wherein the inorganic filler (C) comprises one or two selected from the group consisting of talc, alumina, glass, ceria, mica, diaspore, aluminum hydroxide and magnesium hydroxide. More than one species. A resin substrate containing the cured product of the prepreg according to any one of claims 1 to 10. A metal-clad laminate, which is one-sided or double-sided of the cured product of the prepreg according to any one of claims 1 to 10, or one side of the cured product of the laminate in which the prepreg is overlapped by two or more. Or double-sided, provided with metal foil. The metal-clad laminate according to claim 12, wherein the metal-clad laminate is stored in an environment of 135 ° C and a humidity of 85% RH for 100 hours, and the above-mentioned storage according to JIS C-6481:1996 The peeling strength between the cured product of the prepreg and the metal foil is P ₁ , and the peeling strength between the cured product of the prepreg and the metal foil measured according to JIS C-6481:1996 after storage is set. When it is P ₂ , the rate of change in peel strength represented by 100 × (P _{1 -} P ₂ ) / P ₁ is 30% or less. A printed wiring board obtained by circuit-processing a resin substrate of claim 11 or a metal-clad laminate of claim 12, which is provided with one or two or more circuit layers. In a semiconductor device, a semiconductor element is mounted on the circuit layer of the printed wiring board of claim 14.