JP6880564B2 - Prepregs, resin substrates, metal-clad laminates, printed wiring boards, and semiconductor devices - Google Patents

Description

The present invention relates to prepregs, resin substrates, metal-clad laminates, printed wiring boards, and semiconductor devices.

In recent years, with the demand for higher functionality of electronic devices, high-density integration and high-density mounting of electronic components have been progressing. Further, in order to integrate electronic components at high density and mount them at high density, the miniaturization of semiconductor devices used in these electronic devices is rapidly progressing. A high-density and fine circuit is required for a printed wiring board used in a semiconductor device.

A SAP (semi-additive process) method has been proposed as a method for forming a fine circuit. In the SAP method, first, the surface of the insulating layer is roughened to form an electroless metal plating film as a base on the surface of the insulating layer. Next, the non-circuit-forming portion is protected by plating resist, and the circuit-forming portion is thickened by electrolytic plating. Next, the plating resist is removed, and then the electroless metal plating film other than the circuit forming portion is removed by flash etching to form a circuit on the insulating layer. According to the SAP method, the metal layer laminated on the insulating layer can be thinned, so that finer circuit wiring becomes possible.

The semiconductor device is formed, for example, by mounting a semiconductor element on a printed wiring board. Examples of the technology related to such a printed wiring board include the technology described in Patent Document 1 below. Patent Document 1 describes a printed wiring substrate using a thermosetting resin composition containing a thermosetting resin having a dihydrobenzoxazine ring and a thermosetting resin having a maleimide ring as essential components. In such a thermosetting resin composition, the content ratio of the thermosetting resin having a maleimide ring is 3 to 30 with respect to the total amount of the thermosetting resin having a dihydrobenzoxazine ring and the thermosetting resin having a maleimide ring. It is characterized by being% by weight.

Japanese Unexamined Patent Publication No. 10-259248

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

According to the present invention
A prepreg obtained by impregnating a fiber base material with a thermosetting resin composition.
When thermomechanical analysis measurement was performed on the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours, the average linear expansion calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction of the cured product. The ratio (α ₂ / α _{1 ) of the average coefficient of linear expansion α 2} calculated in the range of 150 ° C. to 250 ° C. to the coefficient α ₁ is 0.7 or more and 2.0 or less, and the above-mentioned average coefficient of linear expansion α _A prepreg in which 2 is 8.0 ppm / ° C. or less is provided.

Further, according to the present invention, there is provided a resin substrate containing a cured product of the prepreg.
Further, according to the present invention, a metal-clad laminate in which a metal foil is provided on one or both sides of a cured product of the prepreg, or on one or both sides of a cured product of a laminate obtained by laminating two or more of the prepregs. A board is provided.

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

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

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

It is sectional drawing which shows an example of the structure of the metal-clad laminated board in this embodiment. It is sectional drawing which shows an example of the structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of the structure of the printed wiring board in this embodiment. It is sectional drawing which shows an example of the structure of the semiconductor device in this embodiment. It is sectional drawing which shows an example of the structure of the semiconductor device in this embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, similar components are designated by a common reference numeral, and the description thereof will be omitted as appropriate. Moreover, the figure is a schematic view and does not match the actual dimensional ratio. Unless otherwise specified, the "~" between the numbers in the sentence indicates the following from the above.
First, the prepreg in the present embodiment will be described.

The prepreg is used to form an insulating layer on a printed wiring board. The prepreg is, for example, in the form of a sheet obtained by impregnating a fiber base material with the thermosetting resin composition (P) (hereinafter, also referred to as resin composition (P)) in the present embodiment and then semi-curing it. It is a 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 heating and curing one prepreg. The resin substrate can also be obtained by heat-curing a laminate in which two or more prepregs are laminated. Further, as the resin substrate, a layer made of a fiber base material constituting the prepreg and an insulating material other than the resin composition (P) may be provided on one side or both sides of the prepreg. Examples of such a layer include a hard coat layer for improving the scratch resistance of the resin substrate. The resin substrate having the hard coat layer can be obtained, for example, by adhering the hard coat layer on one side or both sides of the cured product of the above-mentioned prepreg via the primer layer. Alternatively, a resin substrate may be obtained by curing the prepreg and fusing the prepreg and the hard coat layer by heat treatment with the hard coat layer adhered to one side or both sides of the prepreg before curing. it can.

The prepreg can be used, for example, to form an insulating layer in a build-up layer or an insulating layer in a core layer of a printed wiring board.

When the prepreg is used to form an insulating layer in the core layer of a printed wiring board, for example, two or more prepregs are stacked and the obtained laminate is heat-cured to obtain an insulating layer for the core layer. You can also do it.

The prepreg satisfies the following conditions from the viewpoint of enhancing the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board. That is, when a thermomechanical analysis measurement was performed on a cured product obtained by heating the prepreg at 230 ° C. for 2 hours (hereinafter, also simply referred to as “cured product”), the cured product was 50 in the in-plane direction. The ratio (α ₂ / α _{1 ) of the average coefficient of linear expansion α 2} calculated in the range of 150 ° C to 250 ° C to _{the average coefficient of linear expansion α 1} calculated in the range of ° C to 150 ° C is 0.7 or more and 2.0. It is as follows. Further, α ₂ / α ₁ is preferably 0.75 or more and 1.5 or less, and more preferably 0.8 or more and 1.2 or less.

The cured product of the above-mentioned prepreg can be obtained by simply heating the prepreg at a predetermined temperature (230 ° C.), but the cured product obtained by heating under pressurized conditions is preferable. This is because the cured product formed by heating and pressurizing the prepreg has more stable physical properties and enables accurate evaluation of the physical properties. When the prepreg is heated and pressed to form a cured product, the cured product can be obtained by heating and pressurizing at 4 MPa and 230 ° C. for 2 hours, for example.

Further, the resin substrate composed of only the cured product of the prepreg satisfies the same conditions as the cured product of the prepreg described above. When the resin substrate has a layer other than the cured product of the prepreg, only the cured product of the prepreg needs to satisfy the above conditions. In the following description, the matters mentioned as the conditions for the cured product of the prepreg are also the conditions to be satisfied by the cured product of the prepreg contained in the resin substrate.

In the present embodiment, the average linear expansion coefficients α ₁ and α ₂ are in a temperature range of 30 ° C. to 260 ° C. with respect to the object using a TMA (thermomechanical analysis) device (manufactured by TA Instruments, Q400). It is an average value of the coefficient of linear expansion (CTE) in the plane direction (XY direction) measured under the conditions of ° C., a heating rate of 10 ° C./min, a load of 10 g, and a compression mode.

_{When α 2} / α ₁ satisfies the above range in the cured product, even if a large change occurs in the environmental temperature of the obtained printed wiring board, it occurs due to the difference in the coefficient of linear expansion between the circuit layer and the insulating layer. It is possible to reduce the change in stress. Therefore, even when the obtained printed wiring board or semiconductor device is left in a state where the temperature changes drastically 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 the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved by using such a prepreg.

_{Further, when α 2} / α ₁ satisfies the above range in the cured product, even if a large change occurs in the environmental temperature of the obtained semiconductor device, it is caused by the difference in the coefficient of linear expansion between the printed wiring board and the semiconductor element. The change in stress generated can be reduced. As a result, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and the temperature cycle reliability between the semiconductor element and the printed wiring board at high temperatures can be further improved.

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

When the average coefficient of linear expansion α _{2 of the} cured product satisfies the above range, the difference in the coefficient of linear expansion between the circuit layer and the insulating layer when the obtained printed wiring board is exposed to a high temperature such as solder reflow. The resulting stress can be reduced. Therefore, even when the obtained printed wiring board or semiconductor device is left in a state where the temperature changes drastically for a long period of time, the adhesion between the circuit layer and the insulating 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.

Further, when the average coefficient of linear expansion α _{2 of} the cured product satisfies the above range, the coefficient of linear expansion between the printed wiring board and the semiconductor element when the obtained semiconductor device is exposed to a high temperature such as solder reflow. The stress generated due to the difference can be reduced. As a result, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and the temperature cycle reliability between the semiconductor element and the printed wiring board at high temperatures can be further improved.

Further, from the viewpoint of enhancing the insulation reliability of the printed wiring board under high temperature and high humidity and the connection reliability between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the following conditions. _{That is, when thermomechanical analysis measurement was performed on the cured product, 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. was 7.5 ppm / ° C. or less. It is preferably 7.2 ppm / ° C. or lower, more preferably 6.5 ppm / ° C. or lower. The lower limit is not particularly limited, but may be, for example, 0.1 ppm / ° C. or higher.

When the average coefficient of linear expansion α ₁ satisfies the above range in the cured product, even if a large change occurs in the environmental temperature of the obtained printed wiring board, it is caused by the difference in the coefficient of linear expansion between the circuit layer and the insulating layer. The generated stress can be reduced. Therefore, even when the obtained printed wiring board or semiconductor device is left in a state where the temperature changes drastically for a long period of time, the adhesion between the circuit layer and the insulating 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.

Further, when the average coefficient of linear expansion α ₁ satisfies the above range in the cured product, it is caused by the difference in the coefficient of linear expansion between the printed wiring substrate and the semiconductor element when the obtained semiconductor device is exposed to a high temperature. Therefore, the stress generated can be further reduced. As a result, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and the temperature cycle reliability between the semiconductor element and the printed wiring board at high temperatures can be further improved.

In order to achieve such average linear expansion coefficients α ₁ , α ₂ , and α ₂ / α ₁ , the types of components of the resin composition (P) of the prepreg, the blending amount of each component, the method for producing the prepreg, etc. It is important to set properly. Specifically, the constituent components of the resin composition (P) are a maleimide compound (A), a benzoxazine compound (B), an inorganic filler (C), an epoxy resin (D), and a low-stress material, which will be described later. (E), fiber base material, curing accelerator, etc.

Further, from the viewpoint of further enhancing the connection reliability between the semiconductor element and the printed wiring board, the prepreg preferably satisfies the following conditions. That is, a thermomechanical analysis measurement is performed on the cured product using a thermomechanical analyzer, which includes a process of raising the temperature from 30 ° C. to 260 ° C. at 10 ° C./min and a process of holding the cured product at 260 ° C. for 1 hour. when in, the longitudinal length of the cured product before thermal mechanical analysis measurements as a reference length L _0, the maximum amount of thermal expansion from the reference length L ₀ of the cured product as L _1, 1 a cured product at 260 ° C. When the amount of thermal expansion from _{the reference length L 0} when held for a long time _{is L 2} , the dimensional shrinkage indicated by 100 × (L _{1 −} L ₂ ) / L ₀ is 0.15% or less. It is preferably 0.10% or less, and more preferably 0.10% or less. The lower limit value is not particularly limited, but can be, for example, 0.00% or more.
The vertical direction of the cured product refers to the transport direction of the prepreg (so-called MD).

Generally, when a 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 substrate when the prepreg is heat-cured) is released. The insulating layer tries to shrink. Further, when the resin component of the insulating layer is cooled from a high temperature to a room temperature, the resin component of the insulating layer tends to shrink. On the other hand, when the dimensional shrinkage of the cured product satisfies the above range, the stress generated due to the shrinkage of the insulating layer in the printed wiring board when the obtained semiconductor device is exposed to a high temperature. Can be reduced. Therefore, even when the semiconductor device is left in a state where the temperature changes drastically 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. Further, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and the 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 shrinkage rate, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), and the epoxy resin (D), which are constituents of the resin composition (P), are used. It is important to appropriately control the types and amounts of the low-stress material (E), the fiber base material, the curing accelerator, etc., and the method for producing the prepreg.

Further, the cured product has a process of raising the temperature of the cured product from 30 ° C. to 300 ° C. at 10 ° C./min and a process of lowering the temperature of the cured product from 300 ° C. to 30 ° C. at 10 ° C./min. when performing thermomechanical analysis measured in the plane direction in the compressed mode, a vertical direction of the cured product at 30 ° C. in the course of the longitudinal length of the cured product before thermal mechanical analysis measurements as a reference length L _0, the temperature is decreased When the length of is L ₁ , the dimensional change rate represented by 100 × (L _{1 −} L ₀ ) / L ₀ is preferably −0.20% or more, more preferably −0.15% or more. The lower limit value is not particularly limited, but can be, for example, 0.00% or less.
The vertical direction of the cured product refers to the transport direction of the prepreg (so-called MD).

When the dimensional change rate of the cured product satisfies the above range, the stress generated due to the dimensional change of the insulating layer in the printed wiring board when the obtained semiconductor device is exposed to a severe temperature change is reduced. be able to. Therefore, even when the semiconductor device is left in a state where the temperature changes drastically 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. Further, the displacement of the semiconductor element with respect to the printed wiring board can be further suppressed, and the connection reliability and the 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, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), and the epoxy resin (D), which are constituents of the resin composition (P), are used. It is important to appropriately control the types and amounts of the low-stress material (E), the fiber base material, the curing accelerator, etc., and the method for producing the prepreg.

Further, from the viewpoint of improving the rigidity and heat resistance of the obtained printed wiring board, the prepreg preferably satisfies the following conditions. That is, when the dynamic viscoelasticity of the cured product is measured under the conditions of 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, preferably 270 ° C. The temperature is more preferably 280 ° C. or higher, and even more preferably 280 ° C. or higher. The upper limit is preferably 400 ° C. or lower, for example. The glass transition temperature can be measured using a dynamic viscoelastic analyzer (DMA).

When the glass transition temperature of the cured product by dynamic viscoelasticity measurement satisfies the above range, the rigidity of the obtained printed wiring board is increased, and the warp of the printed wiring board at the time of mounting can be further reduced. As a result, in the obtained semiconductor device, the displacement of the semiconductor element 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, a maleimide compound (A), a benzoxazine compound (B), an inorganic filler (C), and an epoxy resin (D), which are constituents of the resin composition (P), are used. It is important to appropriately control the types and amounts of the low-stress material (E), the fiber base material, the curing accelerator, etc., and the method for producing the prepreg.

Further, 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, for the cured product, when subjected to dynamic viscoelasticity measurement, the storage modulus E _'30 at 30 ° C. of the cured product is preferably at least 10 GPa, more preferably not less than 20GPa .. The upper limit value is not particularly limited, but 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, rigidity and heat resistance of the printed wiring board obtained improves the performance balance of the stress relaxation ability, warping of the printed wiring board when mounting It can be further reduced. Therefore, in the obtained semiconductor device, the displacement 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.

Further, 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, for the cured product, when subjected to dynamic viscoelasticity measurement, the ratio of ₃₀ 'the storage modulus E at 30 ° C. for _250' the storage modulus E at 250 ° C. of a cured product (E _'30 / E _'250) is preferably 1.05 or more 1.75 or less.

In the cured product, the _{E '30 /} E' ₂₅₀ satisfies the above range, can be further suppress a change in the elastic modulus of the printed wiring board to a temperature change. As a result, even if a large temperature change occurs, the insulating layer is less likely to be deformed, and the 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.

To achieve such a storage modulus E _'30 and E' ₃₀ / E _'250 is a constituent of the resin composition (P), a maleimide compound (A), benzoxazine compound (B), inorganic It is important to appropriately control the types and amounts of the filler (C), epoxy resin (D), low-stress material (E), fiber base material, curing accelerator, etc., and the method for producing the prepreg.

Further, from the viewpoint of further improving the fine wiring workability of the cured product of the prepreg or the resin substrate, the prepreg preferably satisfies the following conditions. That is, the mass of the cured product after drying at 120 ° C. for 1 hour is defined as the first mass, and the mass of the cured product after being treated under the following conditions and then dried at 120 ° C. for 1 hour is defined as the second mass. Then, the amount of film thinning defined by [{(first mass)-(second mass)} / (sum of the areas of both the front and back surfaces of the cured product)] × 100 is 1.2 g / m ² or less. Is preferable.
<Conditions>
The cured product is immersed in a 3 g / L sodium hydroxide solution (solvent: diethylene glycol monobutyl ether 11.1% by volume, ethylene glycol 3.6% by volume, pure water 85.3% by volume) at 60 ° C. for 5 minutes. Inflate. Next, the swollen cured product is roughened by immersing it in a roughening aqueous solution (sodium permanganate 60 g / L, sodium hydroxide 45 g / L) at 80 ° C. for 5 minutes. Next, the roughened cured product was immersed in a neutralizing solution (98 mass% sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, pure water 94.2% by volume) at 40 ° C. for 5 minutes. Neutralize the cured product.

When the amount of film reduction 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. This is because the cured product or resin substrate of the prepreg whose film thinning amount defined by the above formula is not more than the above upper limit value can maintain the adhesion to the metal layer (circuit layer) even if the surface is roughened. It is thought that it is from.

In order to achieve such a film-reducing amount, the maleimide compound (A), the benzoxazine compound (B), the inorganic filler (C), and the epoxy resin (D), which are constituents of the resin composition (P), are used. It is important to appropriately control the types and amounts of the low-stress material (E), the fiber base material, the curing accelerator, etc., and the method for producing the prepreg.

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

FIG. 1 is a cross-sectional view showing an example of the configuration of the metal-clad laminate 200 according to the present embodiment. As shown in FIG. 1, the metal-clad laminate 200 is provided with metal foils 105 on both sides of an insulating layer 301 made of a cured product of a prepreg. The metal-clad laminate 200 can be used to form an insulating layer of a printed wiring board. Although the metal foil 105 is provided on both sides of the insulating layer 301 in FIG. 1, the metal-clad laminate 200 of the present embodiment has a configuration in which the metal foil 105 is provided on one side of the insulating layer 301. It may be. Further, the insulating layer 301 may be composed of a cured product of a laminated body in which a plurality of (two or more) prepregs are superposed.

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

When the peel strength change rate of the metal-clad laminate 200 satisfies the above range, the insulation reliability of the obtained printed wiring board under high temperature and high humidity can be improved. This is because the metal-clad laminate 200 whose peel strength change rate defined by the above formula is equal to or less than the above upper limit value maintains adhesion to the metal layer (circuit layer) even when exposed to high temperature and high humidity for a long period of time. It is thought that it can be done.

In order to achieve such a peel strength change rate, a maleimide compound (A), a benzoxazine compound (B), an inorganic filler (C), and an epoxy resin (D), which are constituents of the resin composition (P), are used. ), The type and compounding amount of the low-stress material (E), the fiber base material, the curing accelerator, etc., the method for producing the prepreg, the method for producing the metal-clad laminate 200, and the like are important to be appropriately controlled.

Next, a method for manufacturing the prepreg will be described.
The prepreg is, for example, a sheet-like material obtained by impregnating a fiber base material with the resin composition (P) of the present embodiment and then semi-curing it. A sheet-like material having such a structure is excellent in various properties such as dielectric properties, mechanical and electrical connection reliability under high temperature and humidity, and is suitable for manufacturing 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, but for example, the 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 resin varnish to the fiber base material by various coaters, a method of spraying the resin varnish onto the fiber base material by spraying, and a resin layer (P) composed of the resin composition (P) from both sides of the fiber base material. Examples thereof include a method of laminating a fiber base material in.

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

First, the metal foil 105 is laminated on both the upper and lower sides or one side of the outer side of the laminated body in which two or more prepregs or prepregs are laminated. Next, they are joined under high vacuum conditions using a laminator device or a Becquerel device. In addition, without using a laminator device or a becquerel device, the metal leaf 105 may be simply stacked on the upper and lower sides or one side of the outer side of the laminated body in which two or more prepregs or prepregs are stacked.

Next, the metal-clad laminate 200 can be obtained by heat-press molding a laminate in which a prepreg (or a laminate of two or more prepregs) and a metal foil 105 are laminated. Here, it is preferable to continue the pressurization until the end of cooling during the heat pressurization molding.

The heating temperature during the above heat and pressure molding is preferably 120 ° C. or higher and 250 ° C. or lower, and more preferably 150 ° C. or higher and 240 ° C. or lower.

The pressure during the above heat and pressure molding is preferably 0.5 MPa or more and 5 MPa or less, and more preferably 2.5 MPa or more and 5 MPa or less.

Further, after heat and pressure molding, post-curing may be performed in a constant temperature bath or the like, if necessary. The post-curing temperature is preferably 150 ° C. or higher and 300 ° C. or lower, and more preferably 250 ° C. or higher and 300 ° C. or lower.

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

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

Examples of the metals constituting the metal foil 105 include copper, copper-based alloys, aluminum, aluminum-based alloys, silver, silver-based alloys, gold, gold-based alloys, zinc, zinc-based alloys, nickel, nickel-based alloys, tin, and the like. Examples thereof include tin-based alloys, iron, iron-based alloys, Coval (trade name), 42 alloys, Inver, Super Inver and other Fe—Ni based alloys, W, Mo and the like. Among these, copper or a copper alloy is preferable as the metal constituting the metal foil 105 because it is excellent in conductivity, circuit formation by etching is easy, and it is inexpensive. That is, as the metal foil 105, a copper foil is preferable.

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, more preferably 1.5 μm or more and 18 μm or less.

Next, the fiber base material used in this embodiment will be described.
The fiber base material is not particularly limited, but is a glass fiber base material such as a glass woven cloth or a glass non-woven fabric; a polyamide resin fiber such as a polyamide resin fiber, an aromatic polyamide resin fiber, or a total aromatic polyamide resin fiber; a polyamide resin fiber; a polyester resin fiber. , Aromatic polyester resin fiber, polyester resin fiber such as total aromatic polyester resin fiber; synthetic fiber base material composed of woven fabric or non-woven fabric mainly composed of either polyimide resin fiber or fluororesin fiber; kraft paper , Cotton linter paper, or a paper base material containing a mixed paper of linter and kraft pulp as a main component; and the like. Any of these can be used. Among these, a glass fiber base material is preferable. As a result, a resin substrate having low water absorption, high strength, and low thermal expansion 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 further preferably 12 μm or more and 90 μm or less. By using a fiber base material having such a thickness, the handleability at the time of producing a prepreg can be further improved.

When the thickness of the fiber base material is not more than the above upper limit value, the impregnation property of the resin composition (P) in the fiber base material is improved, and the generation of strand voids and the decrease in insulation reliability can be suppressed. Further, it is possible to facilitate the formation of through holes in the resin substrate or the insulating layer 301 by a laser such as carbon dioxide gas, UV, or excimer. Further, when the thickness of the fiber base material is at least the above lower limit value, the strength of the fiber base material and the prepreg can be improved. As a result, the handleability can be improved, the prepreg can be easily produced, and the warp of the resin substrate can be suppressed.

As the glass fiber base material, for example, glass fiber formed of one or more kinds of glass selected from E glass, S glass, D glass, T glass, NE glass, UT glass, L glass, HP glass and quartz glass. A base material is preferably used.

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

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

（式（１）において、ｎ_１は０以上１０以下の整数であり、Ｘ_１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、式「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である）

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

（上記式（１ａ）において、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は０以上の整数である）

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

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

Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decanylene group, trimethylene group and tetramethylene group. Examples include a group, a pentamethylene group, a hexamethylene group and the like.

Specific examples of the branched alkylene group include -C (CH ₃ ) _2- (isopropylene group), -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -C. Alkylmethylene groups such as (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) _{2- ; -CH (CH 3)} ) CH _2- , -CH (CH ₃ ) CH (CH ₃ )-, -C (CH ₃ ) ₂ CH _2- , -CH (CH ₂ CH ₃ ) CH _2- , -C (CH ₂ CH ₃ ) ₂ -CH ₂ - such as an alkyl ethylene group such as and the like.

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

Further, R ₁ is independently a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, but is a hydrocarbon group having 1 or 2 carbon atoms, specifically, for example, a methyl group or an ethyl group. Is preferable.

Further, a is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0. Further, b is an integer of 0 or more and 3 or less, preferably 0 or 1, and 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. preferable. Also, the maleimide compound (A) is more preferably n ₁ in formula (1) contains at least one or more compounds. As a result, the insulating layer obtained from the resin composition (P) exhibits more excellent heat resistance.

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

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

Specifically, examples of the hydrocarbon group having an aromatic ring and having 6 to 30 carbon atoms include fragrances such as benzene, biphenyl, naphthalene, anthracene, fluorene, phenalene train, indacene, terphenyl, acenaphthylene and phenalene. Examples thereof include a divalent group obtained by removing two hydrogen atoms from the nucleus of a compound having a group property.

Moreover, these aromatic hydrocarbon groups may have a substituent. Here, the term that the aromatic hydrocarbon group has a substituent means that a part or all of the hydrogen atoms constituting the aromatic hydrocarbon group are substituted with the substituent. Examples of the substituent include an alkyl group.

The alkyl group as the substituent is preferably a chain alkyl group. Further, the carbon number thereof 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, a sec-butyl group and the like.

Such a group Y preferably has a group obtained by removing two hydrogen atoms from benzene or naphthalene, and examples of the group represented by the above formula (1a) include the following formulas (1a-1) and (1a-2). ) Is preferable. As a result, the insulating layer obtained from the resin composition (P) exhibits more excellent heat resistance.

The formula (1a-1), in (1a-2), _{R 4} are each independently 1 or 6 carbon atoms or less hydrocarbon groups. e is an integer of 0 or more and 4 or less, more preferably 0, respectively.

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

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

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

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

Examples of such maleimide compound (A2) include 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, hexamethylenediamine bismaleimide, N, N'-1,2-ethylene bismaleimide, and N. , N'-1,3-propylene bismaleimide, N, N'-1,4-tetramethylene bismaleimide and other aliphatic bismaleimide compounds; imide-extended bismaleimide and the like can be mentioned. Of these, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane and imide-extended bismaleimide are particularly preferable. The maleimide compound (A2) may be used alone or in combination of two or more.

Examples of the imide-extended bismaleimide include a bismaleimide compound represented by the following formula (a1), a bismaleimide compound represented by the following formula (a2), and a bismaleimide compound represented by the following formula (a3). Can be mentioned. Specific examples of the bismaleimide compound represented by the formula (a1) include BMI-1500 (manufactured by Digigner Moleculars, molecular weight 1500) and the like. Specific examples of the bismaleimide compound represented by the formula (a2) include BMI-1700 (manufactured by Digigner Moleculars, molecular weight 1700), BMI-1400 (manufactured by Digigner Moleculars, molecular weight 1400) and the like. Be done. Specific examples of the bismaleimide compound represented by the formula (a3) include BMI-3000 (manufactured by Digigner Moleculars, molecular weight 3000) and the like.

（上記式（ａ１）において、ｎは１以上１０以下の整数を示す。）

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

（上記式（ａ２）において、ｎは１以上１０以下の整数を示す。）

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

（上記式（ａ３）において、ｎは１以上１０以下の整数を示す。）

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

The content of the maleimide compound (A) contained in the resin composition (P) is not particularly limited, but when the total solid content (that is, the component excluding the solvent) of the resin composition (P) is 100% by mass. , 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, and 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 shrinkage property and the chemical resistance of the obtained cured product of the prepreg and the resin substrate can be further improved.

The content of the maleimide compound (A1) contained in the maleimide compound (A) is not particularly limited, but is 30.0 when the maleimide compound (A) contained in the resin composition (P) is 100% by mass. It is preferably mass% or more and 100.0 mass% or less, and more preferably 50 mass% or more and 100.0 mass% or less. When the content of the maleimide compound (A1) is within the above range, the balance between the low heat shrinkage and the chemical resistance of the obtained cured product of the prepreg and the resin substrate can be further improved.

The lower limit of the weight average molecular weight (Mw) of the maleimide compound (A1) is not particularly limited, but is preferably 400 or more, and particularly preferably 800 or more. When Mw is at least the above lower limit value, it is possible to suppress the occurrence of tackiness in the prepreg. The upper limit of Mw is not particularly limited, but is preferably 4000 or less, and more preferably 2500 or less. When Mw is not more than the above upper limit value, the impregnation property into the fiber base material is improved at the time of producing the resin substrate, and a more uniform resin substrate can be obtained. The Mw of the maleimide compound (A1) can be measured by, for example, GPC (gel permeation chromatography, standard substance: polystyrene conversion).

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

（上記式（２）において、Ｘ_２はそれぞれ独立に炭素数１以上１０以下のアルキレン基、上記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、式「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_２はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ｃはそれぞれ独立に０以上４以下の整数である）

(In the above formula (2), X ₂ is an alkylene group having 1 to 10 carbon atoms independently, a group represented by the above formula (1a), a group represented by the formula "-SO _2- ", and a formula ". It is a group represented by "-CO-", an oxygen atom or a single bond, R ₂ is a hydrocarbon group having 1 or more carbon atoms and 6 or less carbon atoms, and c is an integer of 0 or more and 4 or less independently. )

（上記式（３）において、Ｘ_３はそれぞれ独立に炭素数１以上１０以下のアルキレン基、上記式（１ａ）で表される基、式「−ＳＯ_２−」で表される基、式「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_３はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ｄはそれぞれ独立に０以上４以下の整数である）

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

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

As such a benzoxazine compound (B), among the compound represented by the above formula (2) and the compound represented by the above formula (3), the compound represented by the above formula (2) is preferable. As a result, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkage and chemical resistance.

Further, in the compound represented by the above formula (2), the above X ₂ is a linear or branched alkylene group having 1 or more carbon atoms and 3 or less carbon atoms, and R ₂ is a hydrocarbon group having 1 or 2 carbon atoms. It is preferable that c is an integer of 0 or more and 2 or less. Alternatively, X ₂ is a group represented by any of the formulas (1a-1) and (1a-2), and c is preferably 0. As a result, the insulating layer obtained from the resin composition (P) exhibits more excellent low heat shrinkage and chemical resistance.

Preferred specific examples of the benzoxazine compound (B) include, for example, a compound represented by the following formula (2-1), a compound represented by the following formula (2-2), and a compound represented by the following formula (2-3). , One or more selected from the compound represented by the following formula (3-1), the compound represented by the following formula (3-2), and the compound represented by the following formula (3-3).

（上記式（２−３）において、Ｒはそれぞれ独立に炭素数１〜４の炭化水素基である）

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

The content of the benzoxazine compound (B) contained in the resin composition (P) is not particularly limited, but the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When, 1.0% by mass or more and 25.0% by mass or less is preferable, and 2.0% by mass or more and 15.0% by mass or less is more preferable. When the content of the benzoxazine compound (B) is within the above range, the low heat shrinkage and chemical resistance of the obtained cured product of the prepreg and the resin substrate can be further improved.

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

The resin composition (P) according to the present embodiment can further contain an epoxy resin (D).
Examples of the epoxy resin (D) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol M type epoxy resin (4,4'-(1,3-). Phenirangeisopridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4' − Cyclohexadiene bisphenol type epoxy resin) and other bisphenol type epoxy resins; phenol novolac type epoxy resin, cresol novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, novolac type epoxy resin having a fused ring aromatic hydrocarbon structure Novolak type epoxy resin such as; biphenyl type epoxy resin; xylylene type epoxy resin, biphenyl aralkyl type epoxy resin and other aralkyl type epoxy resin; naphthylene ether type epoxy resin, naphthol type epoxy resin, naphthalenediol type epoxy resin, bifunctional or Naphthalene type epoxy resin such as tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; norbornene type epoxy resin; adamantan type epoxy resin ; Fluorene type epoxy resin and the like can be mentioned.

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

Among the epoxy resins (D), bisphenol type epoxy resin, novolac type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthalene type from the viewpoint of further improving the heat resistance and insulation reliability of the obtained printed wiring board. One or more selected from the group consisting of epoxy resin, anthracene type epoxy resin, and dicyclopentadiene type epoxy resin is preferable, and aralkyl type epoxy resin, novolac type epoxy resin having a fused ring aromatic hydrocarbon structure, and naphthalene type One or more selected from the group consisting of epoxy resins is more preferable.

As the bisphenol A type epoxy resin, "Epicoat 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, "EPICLON 830S" manufactured by DIC Corporation, and the like can be used. As the bifunctional naphthalene type epoxy resin, "HP4032", "HP4032D", "HP4032SS" and the like 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, "NC3000", "NC3000H", "NC3000L", "NC3000S", "NC3000SH", "NC3100" manufactured by Nippon Kayaku Co., Ltd., and "ESN-170" manufactured by Nippon Kayaku Co., Ltd. , And "ESN-480" and the like can be used. As the biphenyl type epoxy resin, "YX4000", "YX4000H", "YX4000HK", "YL6121" and the like manufactured by Mitsubishi Chemical Corporation can be used. As the anthracene type epoxy resin, "YX8800" manufactured by Mitsubishi Chemical Corporation or the like can be used. As the naphthylene ether type epoxy resin, "HP6000", "EXA-7310", "EXA-7311", "EXA-7311L", "EXA7311-G3" and the like manufactured by DIC Corporation can be used.

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

Among these epoxy resins (D), an aralkyl type epoxy resin is particularly preferable. Thereby, the heat resistance and flame retardancy of the moisture-absorbing solder 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, it is possible to suppress the occurrence of tackiness in the prepreg. The upper limit of Mw is not particularly limited, but is preferably 20,000 or less, and particularly preferably 15,000 or less. When Mw is not more than the above upper limit value, the impregnation property into the fiber base material is improved at the time of producing 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) may be appropriately adjusted according to the purpose thereof, and is not particularly limited. However, when the total amount of the components excluding the inorganic filler (C) in the resin composition (P) is 100% 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, the handleability is improved and it becomes easy to form a prepreg. When the content of the epoxy resin (D) is not more than the above upper limit value, the strength and flame retardancy of the obtained printed wiring board are improved, the coefficient of linear expansion of the printed wiring board is lowered, and the effect of reducing warpage is improved. May be done.

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

Examples of the inorganic filler (C) include silicates such as talc, calcined clay, unfired clay, mica, and glass; oxides such as titanium oxide, alumina, boehmite, silica, and molten silica; calcium carbonate, magnesium carbonate, and the like. , Hydrotalcite and other carbonates; Hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; Sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite; Zinc borate, barium metaborate, Borates such as aluminum borate, calcium borate, sodium borate; nitrides such as aluminum hydroxide, boron nitride, silicon nitride, carbon nitride; titanates such as strontium titanate and barium titanate can be mentioned. it can.

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

The average particle size 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 size of the inorganic filler (C) is at least the above lower limit value, it is possible to suppress the viscosity of the varnish from becoming excessively high, and it is possible to improve the workability at the time of producing the prepreg. The average particle size of the inorganic filler (C) is not particularly limited, but is preferably 5.0 μm or less, more preferably 2.0 μm or less, and even more preferably 1.0 μm or less. When the average particle size of the inorganic filler (C) is not more than the above upper limit value, phenomena such as sedimentation of the inorganic filler (C) can be suppressed in the varnish, and a more uniform resin layer can be obtained. Further, when the circuit dimension 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, for example, a laser diffraction particle size distribution analyzer (HORIBA Ltd., LA-500) by, measuring the particle size distribution of the particles on a volume basis, the median diameter _{(D 50)} Can be the average particle size.

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

The inorganic filler (C) is preferably silica particles, preferably silica particles having an average particle diameter of 5.0 μm or less, more preferably silica particles having an average particle diameter of 0.1 μm or more and 4.0 μm or less, and 0.2 μm or more and 2.0 μm. The following silica particles are particularly preferred. 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 limited, but the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When, 50.0% by mass or more and 85.0% by mass or less is preferable, and 60.0% by mass or more and 80.0% by mass or less is more preferable. When the content of the inorganic filler (C) is within the above range, the obtained cured product of prepreg and the resin substrate can be made to have lower thermal expansion and lower water absorption.

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

Examples of the low-stress material (E) include (meth) acrylic block copolymers; silicone compounds; acrylonitrile-butadiene rubber modified with carboxyl groups, amino groups, vinyl acrylate groups or epoxy groups; aliphatic epoxy resins; And one or more selected from rubber particles and the like.

The (meth) acrylic block copolymer is a block copolymer containing a (meth) acrylic monomer as an essential monomer component. Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and methacrylic. (Meta) acrylic acid alkyl ester such as t-butyl acid, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate; (meth) acrylic acid ester having an alicyclic structure such as cyclohexylacrylic acid, cyclohexyl methacrylate; methacrylic acid (Meta) acrylic acid ester having an aromatic ring such as benzyl acid; (fluoro) alkyl ester of (meth) acrylic acid such as 2-trifluoroethyl methacrylate; such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. Carboxyl group-containing acrylic monomer having a carboxyl group in the molecule; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-Hydroxybutyl methacrylate, mono (meth) acrylic acid ester of glycerin, etc. A hydroxyl group-containing acrylic monomer having a hydroxyl group in the molecule; glycidyl methacrylate, methylglycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, etc. Acrylic monomer having an epoxy group in the molecule; Allyl group-containing acrylic monomer having an allyl group in the molecule such as allyl acrylate and allyl methacrylate; γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl Silane group-containing acrylic monomer having a hydrolyzable silyl group in a molecule such as triethoxysilane; benzotriazole-based ultraviolet rays such as 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole. Examples thereof include an ultraviolet-absorbing acrylic monomer having an absorbent group.

In the (meth) acrylic block copolymer, a monomer other than the acrylic monomer may be used as a monomer component. Examples of the monomer other than the acrylic monomer include aromatic vinyl compounds such as styrene and α-methylstyrene, conjugated diene such as butadiene and isoprene, and olefins such as ethylene, propylene and isobutylene.

The (meth) acrylic block copolymer is not particularly limited, but for example, a diblock copolymer composed of two polymer blocks, a triblock copolymer composed of three polymer blocks, or four or more. Examples thereof include a multi-block copolymer composed of the polymer blocks of.

Among them, the (meth) acrylic block copolymers include polymer blocks (S) (soft blocks) having a low glass transition temperature (Tg) from the viewpoint of improving heat resistance, light resistance, and crack resistance. A block copolymer in which polymer blocks (H) (hard blocks) having a higher Tg than the polymer block (S) are alternately arranged is preferable, and more preferably, a polymer block (S) is provided in the middle thereof. A triblock copolymer having an HSH structure having polymer blocks (H) at both ends is preferable.

A preferable specific example of the (meth) acrylic block copolymer in the resin composition (P) is, for example, a polymer in which the polymer block (S) is composed of butyl acrylate (BA) as a main monomer. Polymethylmethacrylate-block-polybutylacrylate-block-polymethylmethacrylate terpolymer (PMMA-b-PBA-b), which is a polymer in which the polymer block (H) is composed of methyl methacrylate (MMA) as a main monomer. -PMMA) and the like.

Examples of the (meth) acrylic block copolymer include the trade names "Nanostrength M52N", "Nanostrength M22N", "Nanostrength M51", "Nanostrength M52", and "Nanostrength M53" (Arkema). PMMA-b-PBA-b-PMMA), trade names "Nanostrength E21", "Nanostrength E41" (Arkema, PSt (polystyrene) -b-PBA-b-PMMA) and other commercially available products. It can also be used.

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

The aliphatic epoxy resin is preferably an aliphatic epoxy resin having no cyclic structure other than the glycidyl group, and more preferably a bifunctional or higher aliphatic epoxy resin having two or more glycidyl groups. Such an aliphatic epoxy resin is excellent because the epoxy group is less likely to be oxidized and the elastic modulus is less likely to increase due to thermal 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, silicone particles and the like.

The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which the outer shell layer is made of a glassy polymer and the inner core layer is made of a rubbery polymer, or Examples thereof include particles having a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-shell type rubber particles include Staphyroid AC3832, AC3816N (trade name, manufactured by Ganz Kasei Co., Ltd.), and Metabrene 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 size 0.5 μm, manufactured by JSR Corporation) and the like.

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

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) and a core portion made of silicone mainly composed of two-dimensional crosslinks are tertiary. Examples thereof include core-shell structural particles coated with a former crosslinked silicone. As the silicone rubber fine particles, commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, and Trefil E-600 (manufactured by Toray Dow Corning) are available. Can be used.

The content of the low stress material (E) contained in the resin composition (P) is not particularly limited, but the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass. When, 0.1% by mass or more and 10.0% by mass or less is preferable, and 1.0% by mass or more and 8.0% by mass or less is more preferable. When the content of the low-stress material (E) is within the above range, the stress of the obtained cured product of the prepreg and the resin substrate can be further relaxed, and the adhesion to other members such as the circuit layer can be further improved. Can be made to.

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

The curing accelerator is not particularly limited, and examples thereof include a phosphine compound, a compound having a phosphonium salt, an imidazole compound, and the like, and one or a combination of two or more of these can be used. Among these, imidazole compounds are preferable. Since the imidazole-based compound is a compound having a particularly excellent function as a catalyst, the polymerization reaction between the maleimide compound (A) and the benzoxazine compound (B) can be more reliably promoted.

The imidazole-based compound is not particularly limited, and is, for example, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole. , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 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- Examples thereof include 2-undecylimidazole and 1-cyanoethyl-2-phenylimidazole, and one or a combination of two or more of these can be used. Among these, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, and 2-ethyl-4-methylimidazole are preferable. By using these compounds, the reaction between the maleimide compound (A) and the benzoxazine compound (B) is further promoted, the molding processability is improved, and the heat resistance of the obtained cured product is improved. Be done.

Examples of the phosphine compound include primary phosphine such as ethylphosphine and alkylphosphine such as propylphosphine and phenylphosphine; dialkylphosphine such as dimethylphosphine and diethylphosphine, and secondary phosphine such as diphenylphosphine, methylphenylphosphine and ethylphenylphosphine. Trialkylphosphine such as trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, alkyldiphenylphosphine, dialkylphenylphosphine, tribenzylphosphine, tritrylphosphine, tri-p-styrylphosphine , Tri-trisphine (2,6-dimethoxyphenyl) phosphine, tri-4-methylphenylphosphine, tri-4-methoxyphenylphosphine, tri-2-cyanoethylphosphine and other tertiary phosphines. Of these, tertiary phosphine is preferably used.

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, tetraphenylphosphonium tetra-p-methylphenylborate and butyl. Examples thereof include triphenylphosphonium thiocyanate.

The content of the curing accelerator is preferably 0.01 to 5.0 parts by mass, preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total of the maleimide compound (A) and the benzoxazine compound (B). It is more preferably 0.0 parts by mass, and particularly preferably 0.1 to 1.5 parts by mass. By setting the content of the curing accelerator within 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 contain a coupling agent. The coupling agent may be added directly at the time of preparation of the resin composition (P), or when the resin composition (P) contains the inorganic filler (C), it is added in advance to the inorganic filler (C). You may keep it. By using the coupling agent, the wettability of the interface between the fiber base material or the inorganic filler (C) and each resin can be improved. Therefore, it is preferable to use a coupling agent, and the heat resistance of the obtained cured product of the prepreg or the resin substrate can be improved.

Examples of the coupling agent include a silane coupling agent such as an epoxy silane coupling agent, a cationic silane coupling agent, and an aminosilane coupling agent, a titanate-based coupling agent, and a silicone oil type coupling agent. One type of coupling agent may be used alone, or two or more types may be used in combination.

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

As the silane coupling agent, various compounds can be used, and examples thereof include epoxysilane, aminosilane, alkylsilane, ureidosilane, mercaptosilane, and vinylsilane.

Specific compounds include, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino. Propylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3-Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycydoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, γ-ureidopropyltriethoxysilane, vinyltriethoxysilane, etc. Of these, epoxy silane, mercapto silane, and amino silane are preferable, and primary amino silane or anilino silane is more preferable as the amino silane.

The amount of the coupling agent added is appropriately adjusted according to the specific surface area of the inorganic filler (C), and is not particularly limited, but is 100% by mass of the total solid content (that is, the component excluding the solvent) of the resin composition (P). When it is%, it is preferably 0.01% by mass or more and 1% by mass or less, and more preferably 0.05% by mass or more and 0.5% by mass or less.

When the content of the coupling agent is at least the above lower limit value, the inorganic filler (C) can be sufficiently coated, and the heat resistance of the obtained cured prepreg or resin substrate can be improved. Further, when the content of the coupling agent is not more than the above upper limit value, it is possible to suppress the influence on the reaction, and it is possible to suppress the decrease in the obtained cured product of the prepreg, the bending strength of the resin substrate, and the like.

Further, the resin composition (P) contains pigments, dyes, defoamers, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion scavengers, etc., as long as the object of the present invention is not impaired. Additives other than the above-mentioned components may be added.

Pigments include kaolin, synthetic iron oxide red, cadmium yellow, nickel titanium yellow, strontium yellow, chromium hydroxide-containing, chromium oxide, cobalt aluminate, synthetic ultramarine blue and other inorganic pigments, phthalocyanine and other polycyclic pigments, and azo pigments. And so on.

Examples of the dye include isoindolinone, isoindoline, quinophthalone, xanthene, diketopyrrolopyrrole, perylene, perinone, anthraquinone, indigoid, oxazine, quinacridone, benzimidazolone, violanthrone, phthalocyanine, azomethine and the like.

The resin composition (P) uses various mixers such as an ultrasonic dispersion method, a high-pressure collision type dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation / revolution type dispersion method in various organic solvents. The resin varnish (I) can be obtained by dissolving, mixing and stirring.

Examples of the organic solvent used for the resin varnish (I) include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, and cellsolve. Examples thereof include carbitol, anisole, and N-methylpyrrolidone.

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) into the fiber base material can be further improved.
In the above resin composition (P), the ratio of each component is, for example, as follows.

When the total solid content of the resin composition (P) (that is, the component excluding the solvent) is 100% by mass, the proportion of the maleimide compound (A) is 1.0% by mass or more and 25.0% by mass or less, and benzo. It is preferable that the ratio of the oxazine 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 proportion of the maleimide compound (A) is 5.0% by mass or more and 20.0% by mass or less, the proportion of the benzoxazine compound (B) is 2.0% by mass or more and 15.0% by mass or less, and it is inorganic. It is more preferable that the ratio of the filler (C) is 60.0% by mass or more and 80.0% by mass or less.

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

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

As shown in FIG. 2, the printed wiring board 300 according to the present embodiment may be a single-sided printed wiring board, a double-sided printed wiring board, or a multi-layer printed wiring board. The double-sided printed wiring board is a printed wiring board in which a metal layer 303 is laminated on both sides of the insulating layer 301. A multilayer printed wiring board is a printed circuit board in which two or more metal layers 303 are laminated on an insulating layer 301 via an interlayer insulating layer (also referred to as a build-up layer) by a plating through-hole method, a build-up method, or the like. It is a wiring board.

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

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

When 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 that has been treated with a chemical solution or plasma by a SAP (semi-additive process) method. After the electrolytic metal plating film 308 is applied on 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 attached by electrolytic plating. Then, the metal layer 303 is formed on the metal foil 105 or the insulating layer 301 by removing the plating resist and removing the electroless metal plating film 308 by flash etching.

The circuit dimensions of the metal layer 303 can be 25 μm / 25 μm or less, and particularly 15 μm / 15 μm or less, when expressed in line and space (L / S). Generally, if the circuit size is reduced and the wiring is fine, the insulation reliability between the wirings is lowered. However, the printed wiring board 300 according to the present embodiment can be finely wired with a line and space (L / S) of 15 μm / 15 μm or less, and can be miniaturized to a line and space (L / S) of about 10 μm / 10 μm. Can be achieved.

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, but can be made of, for example, a resin film or a prepreg. Among these, prepreg is a sheet-like material, which has excellent various characteristics such as dielectric properties, mechanical and electrical connection reliability under high temperature and humidity, and is suitable for manufacturing a build-up layer 317 for printed wiring boards. preferable.
As the prepreg, the above-mentioned prepreg is particularly preferable.

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 balance between the mechanical strength and the productivity of the insulating layer 301 is particularly excellent, and the insulating layer 301 suitable for a thin printed wiring board can be obtained.

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

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

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

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

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

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

The chemical treatment is not particularly limited, and examples thereof include a method using an oxidizing agent solution or the like having an organic substance decomposing action. Further, as the plasma treatment, a method of directly irradiating an object with an active species having a strong oxidizing action (plasma, radicals, etc.) to remove organic residue can be mentioned.

Next, the metal layer 303 is formed. The metal layer 303 can be formed, for example, by a semi-additive process (SAP) or a modified semi-additive process (MSAP). Hereinafter, a specific description will be given.

First, an electroless metal plating film 308 is formed on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307 by using an electroless plating method to make both sides of the printed wiring board 300 conductive. Further, the via hole 307 can be appropriately filled with a conductor paste or a resin paste. An example of the electroless plating method will be described. For example, first, a catalyst nucleus is imparted on the surface of the metal foil 105 or the insulating layer 301 or in the via hole 307. The catalyst nucleus is not particularly limited, but for example, a noble metal ion or a palladium colloid can be used. Subsequently, the electroless metal plating film 308 is formed by electroless plating treatment with this catalyst nucleus as a nucleus. For the electroless plating treatment, for example, a solution containing copper sulfate, formalin, a complexing agent, sodium hydroxide and the like can be used. After electroless plating, it is preferable to perform heat treatment at 100 to 250 ° C. to stabilize the plating film. Heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. 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 aperture pattern corresponds to, for example, a circuit pattern. The plating resist is not particularly limited, and known materials can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the plating resist. An example using a photosensitive dry film will be described. For example, a photosensitive dry film is laminated on an electroless metal plating film 308, a non-circuit forming region is exposed and photocured, and an unexposed portion is dissolved and removed with a developing solution. A plating resist is formed by leaving the cured photosensitive dry film.

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

Then, the plating resist is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, 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 is removed. For example, the metal foil 105 and / or the electroless metal plating film 308 can be removed by using soft etching (flash etching) or the like. Here, the soft etching process can be performed, for example, by etching with an etching solution containing sulfuric acid and hydrogen peroxide. As a result, the metal layer 303 can be formed. The metal layer 303 is composed of the metal foil 105 and / or the electroless metal plating film 308, and the electrolytic metal plating layer 309.

Further, the build-up layer 317 is laminated on the printed wiring board 300 as needed, and the steps of interlayer connection and circuit formation by the semi-additive process are repeated to form a multi-layer structure.
From the above, the printed wiring board 300 of this embodiment is obtained.

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

First, the printed wiring board 300 obtained by the above method is prepared. Next, a build-up layer is laminated on the metal layer 303 (circuit layer) of the printed wiring board 300 as needed, and the steps of interlayer connection and circuit formation by a semi-additive process are repeated. Then, if necessary, the solder resist layer 401 is laminated on both sides or one side of the printed wiring board 300.

The method for forming the solder resist layer 401 is not particularly limited, and for example, a method of forming by laminating, exposing, and developing a dry film type solder resist, or a method of pattern printing with a liquid resist and then exposing. And a method of forming a pattern by development.

Subsequently, the semiconductor element 407 is placed on the connection terminal which is a part of the circuit layer of the printed wiring board 300 via the solder bump 410. Next, by performing a reflow process, the semiconductor element 407 is fixed onto the connection terminal via the solder bump 410. Then, by sealing the semiconductor element 407, the solder bump 410, and the like with the sealing material 413, the semiconductor device 400 as shown in FIGS. 4 and 5 can be obtained.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. 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 embodiment, the semiconductor element 407 and the circuit layer of the printed wiring board 300 are connected by solder bumps 410, but the present invention is not limited to this. For example, the semiconductor element 407 and the circuit layer of the printed wiring board 300 may be connected by bonding wires.

Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the examples, "parts" represents "parts by mass" unless otherwise specified. In addition, 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 formula (1), n ₁ is 0 or more and 3 or less, X ₁ is a group represented by "-CH _2- ", a is 0, and b is 0 (BMI-2300, Yamato Kasei). Made by Kogyo Co., Ltd., Mw = 750)
Maleimide Compound 2: Bisphenol A Diphenyl Ether Bismaleimide (BMI-4000, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Maleimide compound 3: 4,4'-diphenylmethanebismaleimide (in formula (1), n ₁ is 0, X ₁ is a group represented by "-CH _2- ", a is 0, b is 0, BMI-1000, manufactured by Yamato Kasei Kogyo Co., Ltd.)
Maleimide Compound 4: 1,6'-Bismaleimide- (2,2,4-trimethyl) Hexane (BMI-TMH, manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Maleimide compound 5: Imide-extended bismaleimide (BMI-1500, bismaleimide compound represented by the formula (a1), manufactured by Digigner Moleculars, molecular weight 1500)

Cyanate ester resin: Prepolymer of bisphenol A disicanate (MEK solution with a solid content of 75% by mass, manufactured by Ronza, BA230S)
Benzoxazine compound 1: A benzoxazine compound represented by the formula (2-1) (Pd-type benzoxazine, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
Benzoxazine compound 2: A benzoxazine compound represented by the formula (3-1) (F-a type benzoxazine manufactured by Shikoku Kasei Kogyo Co., Ltd.)

Epoxy resin 1: Aralkill type epoxy resin (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin 2: Bisphenol F type epoxy resin (EPICLON 830S, manufactured by DIC Corporation)
Epoxy resin 3: Naphthalene diol type epoxy resin (EPICLON HP-4032D, manufactured by DIC Corporation)
Epoxy resin 4: Silsesquioxane type epoxy resin (Compoceran SQ502-8, manufactured by Arakawa Chemical Industry Co., Ltd.)

Phenol resin 1: Novolac type phenol resin (PR-HF-3, manufactured by Sumitomo Bakelite)
Inorganic filler 1: Silica (manufactured by Admatex, SC4050, average particle size 1.1 μm, phenylaminosilane-treated silica slurry)

Low stress material 1: Carboxylic acid-terminated acrylonitrile-butadiene rubber (manufactured by PTI Japan, CTBN1008SP)
Low stress material 2: Amino group-terminated acrylonitrile-butazine rubber (manufactured by PTI Japan, ATBN1300X16)
Low stress material 3: Silicone compound (three-dimensional crosslinked silicone resin containing epoxy group and phenyl group, manufactured by Toray Dow Corning, AY42-119)
Low stress material 4: Silicone compound (silicone epoxy resin, manufactured by Toray Dow Corning, BY16-115)
Low stress material 5: Silicone compound (modified silicone resin having amino groups 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 Alchema, nanostrength M51)

Curing Accelerator 1: 2-Phenylimidazole (manufactured by Shikoku Kasei Co., Ltd., 2PZ-PW)
Curing accelerator 2: Tetraphenylphosphonium tetra-p-tolylborate (manufactured by Hokuko Chemical Industry Co., Ltd., TPP-MK)

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

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

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

(Prepregs 2-22)
The prepregs 2 to 22 were manufactured in the same manner as the prepreg 1 except that the type of the resin varnish was changed as shown in Table 1. However, the solid content concentration of the varnish 19 was adjusted with dimethylformamide from the viewpoint of solubility.

(Example 1)
1. 1. Manufacture of Resin Substrate Ultra-thin copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., Microsin Ex, 2.0 μm) was laminated on both sides of the prepreg 1. Next, a resin substrate was obtained by heat and pressure molding at 4 MPa and 230 ° C. for 2 hours. The thickness of the core layer (the portion made of the resin substrate) of the obtained resin substrate with metal foil was 0.107 mm.

2. Manufacture of Printed Wiring Board First, the ultrathin copper foil layer on the surface of the resin substrate with metal foil obtained in the previous section was roughened by about 1 μm. Then, a carbon dioxide laser was used to form a Φ80 μm through hole for interlayer connection. Next, a resin substrate with a metal foil was placed in a container containing a swelling solution at 60 ° C. (Swelling Dip Securigant P manufactured by Attec Japan Co., Ltd.), immersed for 5 minutes, and then the resin substrate with the metal foil was taken out from the container. .. After that, a resin substrate with a metal foil was placed in a container containing an 80 ° C potassium permanganate aqueous solution (Atotech Japan Co., Ltd., Concentrate Compact CP), immersed for 2 minutes, neutralized, and desmeared in the through hole. Was done. Next, electroless copper plating was performed on the resin substrate with metal foil after the desmear treatment so as to have a thickness of 0.5 μm. Next, a resist layer for electrolytic copper plating was formed so as to have a thickness of 18 μm, and pattern copper plating was performed. Then, it was post-cured by heating at 150 ° C. for 30 minutes. Next, the plating resist was peeled off and the entire surface was flash-etched 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 types of prepregs were changed as shown in Table 2.

In addition, the resin substrates obtained in each of the examples and comparative examples were evaluated as follows. The evaluation results are shown in Table 2.

(1) Glass transition temperature The glass transition temperature was measured using a dynamic viscoelastic analyzer (DMA device, manufactured by TA Instruments, 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 with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of the prepreg. Then, using the obtained cured product of the prepreg, dynamic viscoelasticity measurement was performed at a heating rate of 5 ° C./min and a frequency of 1 Hz. The glass transition temperature was set to the temperature at which tan δ showed the maximum value at a frequency of 1 Hz.

(2) Storage elastic modulus E'
The storage elastic modulus E'was measured using a dynamic viscoelastic analyzer (DMA device, manufactured by TA Instruments, 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 with an etching solution (ferric chloride solution, 35 ° C.) to obtain a cured product of the prepreg.

Based on the cured product of the resulting prepreg, heating rate 5 ° C. / min, with a frequency 1 Hz, performs storage modulus measured at 30 ° C. and 250 ° C., the storage modulus at ₃₀ ℃ E '30, 250 ℃ It was calculated storage modulus E _'250 and E,' ₃₀ / E _'250 at.

(3) Dimensional shrinkage rate First, a 4 mm × 15 mm test piece was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (ferric 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 Instruments, Q400) at a heating rate of 10 ° C./min, a load of 10 g, and a pressure of 30 ° C. under the conditions of a compression mode. A thermomechanical analysis measurement including a process of raising the temperature to 260 ° C. and a process of holding the temperature at 260 ° C. for 1 hour was performed. Then, to determine the thermal expansion amount L ₂ from the reference length L ₀ when the maximum expansion amount L ₁ and cured product of the prepreg from the reference length L ₀ of the cured product of the prepreg was held 1 hour at 260 ° C.. Next, the dimensional shrinkage rate represented by 100 × (L _{1 −} L ₂ ) / L _{0 was calculated.}

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

Next, the obtained cured product of the prepreg was compressed using a thermomechanical analyzer TMA (manufactured by TA Instruments, Q400) in a temperature range of 30 to 260 ° C., a heating rate of 10 ° C./min, a load of 10 g, and compression. Two cycles of thermomechanical analysis (TMA) measurements were performed under mode conditions. _{The average value α 1 of the} coefficient of linear expansion in the plane direction (XY direction) in the range of 50 ° C. to 150 ° C. _{and the average value α 2 of the} coefficient of linear expansion in the plane direction (XY direction) in the range of 150 ° C. to 250 ° C. were calculated. ..
The value of the second cycle was adopted as the expansion coefficient.

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

Next, the mass of the obtained cured product of the prepreg after drying at 120 ° C. for 1 hour was defined as the first mass, and after treating the cured product under the following conditions, the mass of the cured product after drying at 120 ° C. for 1 hour. Is the second mass, and the amount of film reduction defined by [{(first mass)-(second mass)} / (sum of the areas of both the front and back surfaces of the cured product)] × 100 is calculated. did.

<Conditions>
The cured product is immersed in a 3 g / L sodium hydroxide solution (solvent: diethylene glycol monobutyl ether 11.1% by volume, ethylene glycol 3.6% by volume, pure water 85.3% by volume) at 60 ° C. for 5 minutes. Inflate. Next, the swollen cured product is roughened by immersing it in a roughening aqueous solution (sodium permanganate 60 g / L, sodium hydroxide 45 g / L) at 80 ° C. for 5 minutes. Next, the roughened cured product was immersed in a neutralizing solution (98 mass% sulfuric acid 5.0% by volume, hydroxylamine sulfate 0.8% by volume, pure water 94.2% by volume) at 40 ° C. for 5 minutes. Neutralize the cured product

(6) Dimensional change rate First, a 4 mm × 15 mm test piece was cut out from the obtained resin substrate. Next, the copper foil of the test piece was removed with an etching solution (ferric 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 Instruments, Q400) at a heating rate of 10 ° C./min, a load of 10 g, and a pressure of 30 ° C. under the conditions of a compression mode. Thermomechanical analysis measurement was carried out including a process of raising the temperature from 300 ° C. to 300 ° C. at 10 ° C./min and a process of lowering the temperature from 300 ° C. to 30 ° C. at 10 ° C./min. Then, the vertical length of the cured product before the thermomechanical analysis measurement was measured as the reference length L _{0, and the vertical length L 1} of the cured product at 30 ° C. in the process of lowering the temperature was measured. Next, the dimensional change rate represented by 100 × (L _{1 −} L ₀ ) / L _{0 was calculated from the obtained L 0} and L _1.

(7) Peel strength change rate When the obtained resin substrate (metal-clad laminate) is stored in an environment of 135 ° C. and a humidity of 85% RH for 100 hours, it is 100 × (P _{1 −} P ₂ ) / P ₁ . The indicated peel strength change rate was calculated.

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

(8) Evaluation of Insulation Reliability between Fine Lines A build-up material (BLA-3700GS, manufactured by Sumitomo Bakelite Co., Ltd.) was laminated on a fine circuit pattern of L / S = 15/15 μm on a printed wiring board, and then a cured test sample was used. Made. Using this test sample, continuous wet insulation resistance was evaluated under the conditions of 130 ° C., humidity of 85%, and applied voltage of 3.3 V. Incidentally, it was a failure less resistance 10 ⁶ Omega. The evaluation criteria are as follows.

〇: No failure for 500 hours or more Δ: Failure in less than 200 to 500 hours ×: Failure in less than 200 hours

(9) Evaluation of fine wire workability The fine wire workability of the printed wiring board after forming the fine circuit pattern of L / S = 15/15 μm was evaluated by visual inspection and continuity check of the fine wire (circuit) with a laser microscope. The evaluation criteria are as follows.

◎: There is no problem with the shape and continuity of the thin wire 〇: There is a problem with the shape of some of the thin wires, but there is no short circuit or broken wiring, and there is virtually no problem.

(10) Through-hole insulation reliability evaluation In the production of the printed wiring board described above, 20 pairs of interlayer-connected through-holes having a diameter of 80 μm were formed so that the distance between the walls was 80 μm. Next, a build-up material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) was laminated on the circuit pattern, and then a cured test sample was prepared. Using this test sample, continuous wet insulation resistance was evaluated under the conditions of 130 ° C., humidity of 85%, and applied voltage of 5.5 V. Incidentally, it was a failure less resistance 10 ⁶ Omega. The evaluation criteria are as follows.

⊚: No failure for 500 hours or more (good)
〇: There is a failure in less than 200 to 500 hours (substantially no problem)
Δ: There is a failure in less than 200 hours (substantially unusable)
×: There is a failure in less than 100 hours (cannot be used)

(11) Warpage evaluation of semiconductor device A build-up material (BLA-3700GS manufactured by Sumitomo Bakelite Co., Ltd.) was laminated on a printed wiring board after forming a circuit pattern, and then cured. Next, the cured product was circuit-processed by a semi-additive method. A semiconductor element with solder bumps having a length of 10 mm, a width of 10 mm, and a thickness of 100 μm was mounted on the semiconductor element. Next, the semiconductor element was sealed with underfill (CRP-4160G, manufactured by Sumitomo Bakelite Co., Ltd.) and cured at 150 ° C. for 2 hours. Finally, a semiconductor device was manufactured by dicing to 15 mm × 15 mm.

The warp of the obtained semiconductor device at 260 ° C. was evaluated using a temperature-variable laser coordinate measuring machine (manufactured by Hitachi Technology and Service Co., Ltd., model LS220-MT100MT50). The evaluation was performed by installing the semiconductor device with the semiconductor element surface facing down in the sample chamber of the measuring machine, measuring the displacement in the height direction, and setting the value having the largest displacement difference as the amount of warpage. The evaluation criteria are as follows.

⊚: Warp amount is less than 30 μm 〇: Warp amount is 30 μm or more and less than 50 μm ×: Warp amount is 50 μm or more

(12) Heat Cycle Test First, four semiconductor devices obtained in (11) were prepared. These semiconductor devices were treated under the conditions of 85 ° C. and 85% RH for 168 hours, and then treated three times in an IR reflow oven (peak temperature: 260 ° C.). Then, in the atmosphere, the conditions of −55 ° C. (15 minutes) and 125 ° C. (15 minutes) were set as one cycle, and such conditions were performed for 500 cycles. Next, using an ultrasonic imaging device (FS300 manufactured by Hitachi Construction Machinery Finetech Co., Ltd.), it was observed whether or not there were any abnormalities in the semiconductor element and the solder bump.

⊚: No abnormality in semiconductor element and solder bump 〇: Cracks are seen in part of semiconductor element and / or solder bump, but there is no problem in practical use ×: Crack is seen in part or all of semiconductor element and / or solder bump There is a problem in practical use

105 Metal foil 200 Metal-clad laminate 300 Printed wiring board 301 Insulation layer 303 Metal layer 305 Insulation layer 307 Via hole 308 Electrolytic metal plating film 309 Electrolytic metal plating layer 311 Core layer 317 Build-up layer 400 Semiconductor device 401 Solder resist layer 407 Semiconductor Element 410 Solder bump 413 Encapsulant

Claims (13)

A prepreg obtained by impregnating a fiber base material with a thermosetting resin composition.
The thermosetting resin composition contains a maleimide compound (A), a benzoxazine compound (B), and an inorganic filler (C).
The maleimide compound (A) contains 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 X ₁ is an alkylene group having 1 or more and 10 or less carbon atoms independently, a group represented by the following formula (1a), and the formula "-". A group represented by "SO _2- ", a group represented by the formula "-CO-", an oxygen atom or a single bond, and R ₁ is an independently hydrocarbon group having 1 or more and 6 or less carbon atoms. Are independently 0, and b is independently 0)

(In the above formula (1a), Y is a hydrocarbon group having an aromatic ring and having 6 or more and 30 or less carbon atoms, and n ₂ is an integer of 0 or more).
The content of the maleimide compound (A) contained in the thermosetting resin composition is 1.0% by mass or more and 25.0 when the total solid content of the thermosetting resin composition is 100% by mass. It is less than% by mass and
The content of the inorganic filler (C) contained in the thermosetting resin composition is 50.0% by mass or more when the total solid content of the thermosetting resin composition is 100% by mass. It is 0% by mass or less,
When thermomechanical analysis measurement was performed on the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours, the average linear expansion calculated in the range of 50 ° C. to 150 ° C. in the in-plane direction of the cured product. The ratio (α ₂ / α _{1 ) of the average coefficient of linear expansion α 2} calculated in the range of 150 ° C. to 250 ° C. to the coefficient α ₁ is 0.7 or more and 2.0 or less, and the average coefficient of linear expansion α ₂ is a prepreg having a temperature of 8.0 ppm / ° C or less. A thermomechanical machine having a process of raising the temperature of the cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours at 10 ° C./min from 30 ° C. to 260 ° C. and a process of holding the prepreg at 260 ° C. for 1 hour. When performing analytical measurements
The longitudinal length of the cured product before the thermal mechanical analysis measurements as a reference length L _0, the maximum amount of thermal expansion from the reference length L ₀ of the cured product as L _1, the cured product 260 ° C. When the amount of thermal expansion from the _{reference length L 0} when held for 1 hour _{is L 2} .
The prepreg according to claim 1, wherein the dimensional shrinkage rate represented by 100 × (L _{1 −} L ₂ ) / L _{0 is 0.15% or less.} The cured product obtained by heat-treating the prepreg at 230 ° C. for 2 hours is heated from 30 ° C. to 300 ° C. at 10 ° C./min and lowered from 300 ° C. to 30 ° C. at 10 ° C./min. When performing thermomechanical analysis measurements in the plane direction in compression mode with process
The longitudinal length of the cured product before the thermal mechanical analysis measurements as a reference length L _0,
When the vertical length of the cured product at 30 ° C. in the process of lowering the temperature is L ₁ .
The prepreg according to claim 1, wherein the dimensional change rate represented by 100 × (L _{1 −} L ₀ ) / L _{0 is −0.20% or more.} The first aspect of claim 1, wherein the glass transition temperature of the cured product is 260 ° C. or higher when dynamic viscoelasticity measurement is performed on the cured product under the conditions of a temperature rising rate of 5 ° C./min and a frequency of 1 Hz. Prepreg. With respect to the cured product, when subjected to dynamic viscoelasticity measurement, the ratio of ₃₀ 'the storage modulus E at 30 ° C. for _250' the storage modulus E at 250 ° C. of the cured product (E _'30 / E _'250) is, the prepreg according to claim 1, wherein 1.05 or more 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 benzoxazine compound (B) contains one or more selected from the compound represented by the following formula (2) and the compound represented by the following formula (3).

(In the formula (2), X ₂ is an alkylene group having 1 or more and 10 or less carbon atoms, a group represented by the formula (1a), a group represented by the formula "-SO _2- ", and a formula ". It is a group represented by "-CO-", an oxygen atom or a single bond, R ₂ is an independently hydrocarbon group having 1 to 6 carbon atoms, and c is an independently integer of 0 or more and 4 or less).

In (Formula (3), _{X 3} are each independently a number of 1 to 10 alkylene group having a carbon group represented by the formula (1a), wherein "-SO ₂ -" group represented by the formula " It is a group represented by "-CO-", an oxygen atom or a single bond, R ₃ is an independently hydrocarbon group having 1 to 6 carbon atoms, and d is an independently integer of 0 or more and 4 or less). The prepreg according to claim 1, wherein the inorganic filler (C) comprises one or more selected from talc, alumina, glass, silica, mica, boehmite, aluminum hydroxide, and magnesium hydroxide. A resin substrate containing a cured product of the prepreg according to any one of claims 1 to 8. A metal in which a metal foil is provided on one or both sides of a cured product of the prepreg according to any one of claims 1 to 8 , or on one or both sides of a cured product of a laminate obtained by stacking two or more of the prepregs. Zhang laminate. When the metal-clad laminate is stored for 100 hours in an environment of 135 ° C. and 85% humidity RH,
_{Let P 1 be} the peel strength between the cured product of the prepreg and the metal leaf, which is measured in accordance with JIS C-6481: 1996 before storage.
Said storage after JIS C-6481: 1996 are measured according to, when the peel strength between the cured product and the metal foil of the prepreg was P _2,
The metal-clad laminate according to claim 10 , wherein the peel strength change rate represented by 100 × (P _{1 −} P ₂ ) / P _{1 is 30% or less.} A printed wiring board obtained by circuit-processing the resin substrate according to claim 9 or the metal-clad laminate according to claim 10, and provided with one layer or two or more circuit layers. A semiconductor device in which a semiconductor element is mounted on the circuit layer of the printed wiring board according to claim 12.

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