JP6657567B2 - Method for manufacturing resin sheet - Google Patents

Description

  The present invention relates to a method for manufacturing a resin sheet.

  As a technique for manufacturing a printed wiring board, a build-up method of alternately stacking conductor layers and insulating layers formed with circuits is widely used. The insulating layer is generally formed by laminating a resin sheet containing a resin composition layer on an inner layer substrate and curing the resin composition layer.

  In recent years, a laminated sheet including a plurality of resin composition layers having different functions has been disclosed (Patent Document 1 and the like).

JP 2014-17301A

  In the production of such a laminated sheet, it is necessary to produce a plurality of resin composition layers. The resin composition layer is produced by applying a resin varnish containing the resin composition. In order to improve productivity and cost performance, the production speed of the resin composition layer (the application speed of the resin varnish) is increased. The present inventors have found that when the resin composition is raised, the resin varnish becomes easy to repel, and that a problem such as wrinkles or protrusions occurs in the resin composition layer. In particular, it has been found that this problem becomes remarkable when a thin resin composition layer is produced.

  It is an object of the present invention to provide a method for producing a resin sheet which suppresses repelling, wrinkles and protrusions of the resin varnish even when the coating speed of the resin varnish is increased, and is excellent in productivity.

  The present inventors have conducted intensive studies on the above problems, and as a result, found that the above problems can be solved by using a resin varnish in which the specific surface area and the content of the inorganic filler satisfy a predetermined relationship. Reached.

That is, the present invention includes the following contents.
[1] (A) a step of coating a resin varnish on a support;
(B) a step of drying the applied resin varnish to form a resin composition layer;
A method for producing a resin sheet, comprising:
The coating speed Y of the resin varnish is 20 m / min or more,
Resin varnish contains inorganic filler,
When the specific surface area (m ² / g) of the inorganic filler is S and the content (parts by mass) of the inorganic filler is V when the nonvolatile component in the resin varnish is 1 part by mass, A method for producing a resin sheet, wherein a product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Equation (1)
(However, 0.9 ≧ V ≧ 0.003)
[2] The method according to [1], wherein the thickness of the resin composition layer is 5 μm or less.
[3] The method according to [1] or [2], wherein X and Y satisfy the following relational expression (2), where X (m) is the total length of the drying zone in which the step (B) is performed.
Y / X ≧ 0.5 Equation (2)
[4] The method according to any one of [1] to [3], wherein the specific surface area S of the inorganic filler is 5 m ² / g or more.
[5] The method according to any one of [1] to [4], wherein the specific surface area S of the inorganic filler is 5 m ² / g or more and 500 m ² / g or less.
[6] The method according to any one of [1] to [5], wherein the content V of the inorganic filler is 0.5 parts by mass or less.
[7] The method according to any one of [1] to [6], wherein the coating speed Y of the resin varnish is 25 m / min or more.
[8] The method according to any one of [1] to [7], wherein the resin sheet is a circuit-forming resin sheet used by being laminated on an insulating resin layer.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to suppress the generation | occurrence | production of the resin varnish repelling, a wrinkle, and a projection, and to provide the manufacturing method of the resin sheet excellent in productivity, even if increasing the coating speed.

  Hereinafter, a method for manufacturing a resin sheet, a resin sheet, a laminated sheet, a laminated plate, and a semiconductor device of the present invention will be described in detail.

  In the present specification, the repelling of the resin varnish refers to a phenomenon in which the resin varnish is repelled on the coating surface of the resin varnish, and as a result, a region having no resin varnish or a region having an extremely small amount of the resin varnish is formed. In the present specification, the repelling of the resin varnish includes both repelling generated immediately after application of the resin varnish and repelling generated in a process of drying the resin varnish. In this specification, wrinkles refer to streak-like surface defects formed in the resin composition layer, and protrusions refer to protrusion-like surface defects due to aggregates formed in the resin composition layer.

  In the present specification, “high-speed coating” means coating at a coating speed of 20 m / min or more, unless otherwise specified.

[Resin sheet manufacturing method]
The method for producing a resin sheet of the present invention comprises:
(A) a step of coating a resin varnish on the support;
(B) a step of drying the applied resin varnish to form a resin composition layer;
Including
The coating speed Y of the resin varnish is 20 m / min or more,
Resin varnish contains inorganic filler,
When the specific surface area (m ² / g) of the inorganic filler is S and the content (parts by mass) of the inorganic filler is V when the nonvolatile component in the resin varnish is 1 part by mass, The product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Equation (1)
(However, 0.9 ≧ V ≧ 0.003)

  In the present invention, even when the resin varnish is applied at a high speed, the specific surface area S and the content V of the inorganic filler are adjusted so as to satisfy the above relational expression (1), so that the resin varnish repels and wrinkles. It is possible to provide a method for manufacturing a resin sheet that suppresses the occurrence of protrusions and protrusions and is excellent in productivity.

  Hereinafter, each step in the method for producing a resin sheet of the present invention will be described in detail.

<Step (A)>
In the step (A), a resin varnish is applied on the support. In the method for producing a resin sheet of the present invention, a resin varnish is applied at a coating speed of 20 m / min or more.

  As described above, increasing the coating speed of the resin varnish is advantageous for improving productivity and cost performance. However, the coating speed of the resin varnish is generally less than 20 m / min (in many cases, 10 to 15 m / min) due to restrictions such as the length of a drying zone for drying the resin varnish. Was. In detail, since the coating of the resin varnish and the drying of the resin varnish are usually performed on the same line, when the coating speed of the resin varnish is increased, the support after the coating of the resin varnish passes through the drying zone. Your speed will also increase. Therefore, it is necessary to increase the length of the drying zone in order to sufficiently dry the resin varnish. However, the length of the drying zone is limited in terms of equipment design and specifications. Construction speed was limited. A method of rapidly drying the resin varnish by setting the temperature of the drying zone high is also conceivable. However, in such a method, a rapid evaporation of the solvent in the resin varnish occurs, and as a result, repelling occurs in a process of drying the resin varnish. Tended to occur. The present inventors have also found that during high-speed application of a resin varnish, repelling is likely to occur immediately after application of the resin varnish, and problems such as wrinkles and protrusions occur in the resin composition layer. In this regard, in the method for producing a resin sheet of the present invention using a resin varnish in which the specific surface area S and the content V of the inorganic filler satisfy the above relational expression (1), the coating speed Y of the resin varnish is 20 m / min or more. Even in this case, repelling, wrinkles and projections of the resin varnish can be suppressed. In the method for producing a resin sheet according to the present invention, a higher coating speed Y can be employed while suppressing the repelling, wrinkles and projections of the resin varnish. For example, the coating speed Y of the resin varnish may be 25 m / min or more, 30 m / min or more, 35 m / min or more, or 40 m / min or more. In the present invention, the upper limit of the coating speed Y may be usually 300 m / min or less, 200 m / min or less, 100 m / min or less from the viewpoint of sufficiently suppressing the repelling, wrinkles and projections of the resin varnish.

-Resin varnish-
The resin varnish used in the present invention contains an inorganic filler. In the case where the specific surface area (m ² / g) of the inorganic filler is S and the nonvolatile component in the resin varnish is 1 part by mass, from the viewpoint of suppressing the occurrence of repelling, wrinkles and projections during high-speed coating of the resin varnish, Assuming that the content (parts by mass) of the inorganic filler is V, the product (SV) of S and V satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Equation (1)
(However, 0.9 ≧ V ≧ 0.003)

The product (SV) of S and V is 1.5 or more, preferably 2.0 or more, more preferably 3.0 or more, 4.0 or more, from the viewpoint of suppressing the occurrence of repelling of the resin varnish. 5.0 or more. In addition, from the viewpoint of suppressing the occurrence of wrinkles and protrusions, the SV is 100 or less, preferably 95 or less, more preferably 90 or less. More specifically, if the specific surface area S (m ² / g) of the inorganic filler is large, wrinkles and projections are likely to occur, so that the content V (parts by mass) of the inorganic filler may be reduced, and If the specific surface area S (m ² / g) is small, repelling is likely to occur, so that the content V (parts by mass) of the inorganic filler may be increased. The specific specific surface area S (m ² / g) and the content V of the inorganic filler will be described later.

  The resin varnish can be prepared by dissolving a resin composition containing an inorganic filler (details will be described later) in a solvent. The solvent used for preparing the resin varnish is not particularly limited as long as the effect of the present invention is not impaired, and a known solvent that can be used for manufacturing a resin sheet may be used. Examples of the solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethers such as cellosolve, butyl carbitol and propylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbyl. Acetates such as tall acetate; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; alcohols such as ethanol and 2-methoxypropanol; solvent naphtha and the like. Can be mentioned. The solvents may be used alone or in combination of two or more.

  The solvent has a boiling point of 100 ° C or higher (preferably 105 ° C or higher, more preferably 110 ° C or higher, 115 ° C or higher, or (120 ° C. or higher). Therefore, in a preferred embodiment, the solvent includes a solvent having a boiling point of 100 ° C or higher. From the viewpoint of suppressing the occurrence of repelling, wrinkles and projections at the time of high-speed coating of the resin varnish and increasing the value of Y / X described later, the solvent is added to a solvent having a boiling point of 100 ° C. or more and a boiling point of 100 ° C. or more. It is preferable to contain a solvent of less than (preferably 95 ° C. or lower, more preferably 90 ° C. or lower, 85 ° C. or lower, or 80 ° C. or lower). Therefore, in a preferred embodiment, a mixed solvent of a solvent having a boiling point of 100 ° C or higher and a solvent having a boiling point of lower than 100 ° C is used as the solvent.

  The mass ratio of the solvent having a boiling point of 100 ° C. or more to the solvent having a boiling point of less than 100 ° C. [(solvent having a boiling point of 100 ° C. or more) / (solvent having a boiling point of less than 100 ° C.)] is determined in the drying zone in which the step (B) is performed. It is preferably 2/8 to 8/2, and more preferably 3/7 to 7/3, although it depends on the total length of the above and the set temperature.

  The viscosity (23 ° C.) of the resin varnish is preferably 10 mPa · s or more from the viewpoint of suppressing the occurrence of repelling, wrinkles and protrusions, and the ability to easily control the thickness of the resin composition layer even in high-speed coating. Preferably, it is 30 mPa · s or more, more preferably 50 mPa · s or more. The upper limit of the viscosity of the resin varnish is not particularly limited, but is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, and still more preferably 3000 mPa · s or less.

  The viscosity of the resin varnish can be measured, for example, using a rotary (E-type) viscometer. As the rotary (E-type) viscometer, for example, "RE-80U" manufactured by Toki Sangyo Co., Ltd. is exemplified.

  The content of the non-volatile components in the resin varnish is not particularly limited as long as the above-mentioned suitable viscosity can be achieved. For example, the resin varnish can be prepared such that the content of the nonvolatile component in the resin varnish is preferably in a range of 30% by mass to 70% by mass, and more preferably in a range of 40% by mass to 70% by mass.

-Support-
Examples of the support include a film made of a plastic material, a metal foil, and release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. May be used.

  The support may be subjected to a mat treatment or a corona treatment on the surface on which the resin varnish is applied. Further, as the support, a support with a release layer having a release layer on the surface on which the resin varnish is applied may be used. Examples of the release agent used in the release layer of the support having a release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Commercially available release agents include, for example, "SK-1", "AL-5", "AL-7" manufactured by Lintec Co., Ltd., which are alkyd resin release agents.

  The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When the support is a support with a release layer, the thickness of the entire support with a release layer is preferably within the above range.

  The application (application) of the resin varnish may be performed by any conventionally known method as long as a coating film having a uniform thickness can be formed. For example, a resin varnish can be coated on the support using a coating device such as a die coater, a comma coater, a gravure coater, or a bar coater.

<Step (B)>
In the step (B), the applied resin varnish is dried to form a resin composition layer.

  Step (B) can be performed in a drying zone. In the present invention, the “drying zone” means a region where a treatment such as heating and decompression is performed in order to dry the resin varnish applied in the step (A). In a preferred embodiment, drying of the resin varnish is performed by heating the resin varnish to evaporate the solvent.

  Drying conditions may be determined according to the boiling point of the solvent contained in the resin varnish. For example, the drying temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. The upper limit of the drying temperature is not particularly limited, but may be usually 150 ° C. or lower, 140 ° C. or lower.

  Step (B) may be performed using a single drying zone, or may be performed using multiple drying zones. When a plurality of drying zones are used, the number n of the drying zones is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, or 6 or more. Although the upper limit of the number n of the drying zones is not particularly limited, it can be usually 20 or less, 15 or less, 10 or less. When performing step (B) using a plurality of drying zones, the plurality of drying zones may be set to the same drying condition, or may be set to different drying conditions. Hereinafter, the drying zone through which the support obtained in the step (A) first passes is referred to as a “first drying zone”, the drying zone passing through the second time is referred to as “second drying zone”, and the drying zone passing through the nth time is referred to as “drying zone”. Also referred to as “n-th drying zone” (provided that 3 ≦ n ≦ 20).

  When the step (B) is performed using a plurality of drying zones, the temperature T1 of the first drying zone is generally included in the resin varnish from the viewpoint of suppressing repelling of the resin varnish due to rapid evaporation of the solvent. The temperature is set sufficiently lower than the boiling point of the solvent to be used. When the boiling point (° C.) of the solvent having the lowest boiling point contained in the resin varnish is Tb, the temperature T1 of the first drying zone is generally lower than (Tb−10) ° C., (Tb−15) ° C. or lower, or ( Tb-20) It is set to a temperature of not more than ° C. In this regard, in the present invention using the resin varnish satisfying the above relational expression (1), the temperature T1 of the first drying zone can be set high while suppressing the repelling of the resin varnish. In the present invention, the temperature T1 of the first drying zone may be (Tb-10) C or higher, or (Tb-5) C or higher. In the present invention, the upper limit of the temperature T1 of the first drying zone is preferably (Tb + 20) ° C. or lower, more preferably (Tb + 15) ° C. or lower, and further preferably (Tb + 10) ° C. or lower, from the viewpoint of suppressing repelling of the resin varnish. It is. From the viewpoint that the Y / X ratio described later can be set high while suppressing rapid evaporation of the solvent, the temperature T2 of the second drying zone is preferably higher than the temperature T1, and is preferably (T1 + 5) ° C. or higher. The temperature is more preferably (T1 + 10) ° C. or higher. The upper limit of the temperature T2 of the second drying zone is preferably (T1 + 50) ° C or lower, more preferably (T1 + 40) ° C or lower, further preferably (T1 + 30) ° C or lower, or (T1 + 20) ° C or lower. The temperature Tmax of the drying zone set to the highest temperature is preferably (Tb′−50) ° C. or higher, when the boiling point (° C.) of the solvent having the highest boiling point contained in the resin varnish is Tb ′. Preferably it is (Tb'-40) degreeC or more. The upper limit of the temperature Tmax is not particularly limited as long as it is within the above-mentioned preferable range of the drying temperature, but is preferably (Tb '+ 10) C or lower, more preferably (Tb' + 5) C or lower. In a preferred embodiment, the temperature of the drying zone is set to increase in order from the first drying zone to the n-th drying zone.

  Note that a single drying zone that can realize a temperature gradient from the inlet to the outlet may be used. In such an embodiment, the inlet temperature may be the same as the temperature T1, and the maximum temperature in the drying zone may be the same as the temperature Tmax.

  As described above, the application of the resin varnish and the drying of the resin varnish are usually performed on the same line, and the passing speed of the resin sheet in the drying zone is the same as the above-described coating speed Y (m / min).

Assuming that the total length (m) of the drying zone for performing the step (B) is X, from the viewpoint of improving the productivity of the resin sheet, X and Y preferably satisfy the following relational expression (2). The total length of the drying zones refers to the length of the drying zone when using a single drying zone, and refers to the sum of the lengths of the drying zones when using a plurality of drying zones. .
Y / X ≧ 0.5 Equation (2)

  As described above, the coating speed Y of the resin varnish tends to be limited due to the restriction of the total length X of the drying zone. Furthermore, when the coating speed Y of the resin varnish is increased, repelling is likely to occur immediately after the coating of the resin varnish, and defects such as wrinkles and protrusions may occur in the resin composition layer. It was found in. In this respect, in the present invention using the resin varnish satisfying the above relational expression (1), it is possible to realize a higher Y / X ratio while suppressing the repelling, wrinkles and projections of the resin varnish. In the present invention, the Y / X ratio may be 0.6 or more, 0.7 or more, 0.8 or more, 0.9 or more, or 1.0 or more. The upper limit of the Y / X ratio is not particularly limited, but is preferably 10 or less, more preferably 8 or less, and further preferably 5 or less.

  The total length X of the drying zone is not particularly limited as long as the relational expression (2) is satisfied in relation to the coating speed Y, but is preferably 2 to 80 m, more preferably 10 to 50 m, and more preferably 20 to 40 m. More preferred. When a plurality of drying zones are used, the length of each drying zone is not particularly limited, but is preferably 1 m to 10 m, more preferably 2 m to 8 m, and still more preferably 3 m to 7 m.

  Note that it is not always necessary to completely remove the solvent in the step (B). When the content of the non-volatile component in the resin composition layer formed on the support is 100% by mass, preferably 5% by mass or less, more preferably 3% by mass or less, 2% by mass or less, or 1% by mass or less. May contain a solvent.

  In the present invention, by satisfying the above relational expression (1), even when a resin varnish is applied at a high speed to form a thin resin composition layer, repelling, wrinkling and protrusion of the resin varnish are suppressed. can do. For example, even when a resin composition layer as thin as 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 μm or less, 3 μm or less, 2.5 μm or less, or 2 μm or less is formed, the above relational expression (1) The effect of the present invention can be obtained by satisfying the condition (1). The lower limit of the thickness of the resin composition layer is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0.4 μm or more, 0.6 μm or more, 0.8 μm or more, Or it is 1 μm or more. The thickness of the resin composition layer can be measured using, for example, a contact-type layer thickness gauge. Examples of the contact-type layer thickness meter include “MCD-25MJ” manufactured by Mitutoyo Corporation.

<Other steps>
The method for producing a resin sheet of the present invention may include a step of cooling the resin sheet after the step (B) (hereinafter, also referred to as “step (C)”).

  The step (C) may be performed by a known cooling method such as blowing cold air. The specific cooling temperature is preferably less than 50 ° C, more preferably 45 ° C or less, and further preferably 40 ° C or less.

  In the resin sheet manufactured by the method for manufacturing a resin sheet of the present invention, the number of repelled resin varnishes in a length of 20 m is 1 or less, preferably 0, when visually observed. Repelling indicates a dent with a diameter of 1.5 mm or more.

  In the resin sheet manufactured by the method for manufacturing a resin sheet of the present invention, the number of wrinkles and protrusions of the resin composition layer in a length of 20 m is 1 or less, preferably 0, in visual observation. Wrinkles represent those having a length of 3 mm or more, and projections represent those having a diameter of 1.5 mm or more.

  In the method for producing a resin sheet of the present invention, after the step (B), a protective film conforming to the support is applied to a surface of the resin composition layer that is not bonded to the support (that is, a surface opposite to the support). May be provided.

  The thickness of the protective film is not particularly limited, but may be, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and to prevent scratches. The resin sheet can be wound and stored in a roll shape, and can be used by peeling off a protective film when forming an insulating layer in the manufacture of a printed wiring board.

  It is preferable that the protective film is laminated to the resin composition layer by a roll or press-compression. The lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho Co., Ltd., and a vacuum applicator manufactured by Nichigo Morton Co., Ltd.

  The resin sheet manufactured by the method of the present invention is suitable as a resin sheet for forming a circuit used by being laminated on an insulating resin layer. By using the resin sheet in combination with an insulating resin layer when manufacturing a printed wiring board, an insulating layer having a low surface roughness after the roughening treatment can be realized. Above all, it can be particularly preferably used as a resin sheet for forming a circuit by a plating process (resin sheet for forming a circuit by a plating process).

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer bonded to the support.

  The support is as described above. Further, as described above, the resin composition layer is formed by applying a resin varnish satisfying the above relational expression (1) and drying. Hereinafter, the resin composition used for preparing the resin varnish will be described.

  Examples of the resin composition include a composition containing an inorganic filler, a curable resin, and a curing agent thereof. As the curable resin, a conventionally known curable resin used for forming an insulating layer of a printed wiring board can be used, and among them, an epoxy resin is preferable. Thus, in one embodiment, the resin composition comprises (a) an inorganic filler, (b) an epoxy resin, and (c) a curing agent. The resin composition may further contain additives such as (d) an organic filler, (e) a thermoplastic resin, (f) a curing accelerator, and (g) a flame retardant, if necessary.

  Hereinafter, the materials of the resin composition will be described.

-(A) Inorganic filler-
The specific surface area S of the inorganic filler is not particularly limited as long as the above relational expression (1) is satisfied in relation to the content V of the inorganic filler, but from the viewpoint of repelling, preferably 5 m ² / g or more. It is preferably 7 m ² / g or more, 10 m ² / g or more, 20 m ² / g or more, and 30 m ² / g or more, and particularly preferably 40 m ² / g or more from the viewpoint of improving fine wiring formability. From the viewpoint of preventing wrinkles and projections, the thickness is preferably 500 m ² / g or less, more preferably 400 m ² / g or less, and further preferably 350 m ² / g or less. The specific surface area S of the inorganic filler can be measured by the BET method. Specifically, molecules having a known adsorption occupation area are adsorbed on the inorganic filler sample at the temperature of liquid nitrogen, and the specific surface area of the inorganic filler sample can be obtained from the amount of adsorption. As a molecule having a known adsorption occupation area, an inert gas such as nitrogen or helium is preferably used. The specific surface area S of the inorganic filler can be measured using an automatic specific surface area measuring device. As the automatic specific surface area measuring device, for example, “Macsorb HM-1210” manufactured by Mountech Co., Ltd. can be mentioned.

  The content of the inorganic filler when the nonvolatile component in the resin composition is 1 part by mass, that is, the content V of the inorganic filler when the nonvolatile component in the resin varnish is 1 part by mass is 0.003. It is at least 0.9 part by mass and at most 0.9 part by mass. Preferably 0.8 parts by mass or less, more preferably 0.6 parts by mass or less, in particular, in that the plating adhesion is sufficiently improved even in the formation of fine wiring, and in that the occurrence of projections in the formation of a thin film is prevented. Therefore, the content is preferably 0.5 parts by mass or less, 0.4 parts by mass or less, and 0.3 parts by mass or less. The lower limit of the content V is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more.

  Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, and the like, and silica is particularly preferred. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As the silica, spherical silica is preferable. One kind of the inorganic filler may be used alone, or two or more kinds may be used in combination. Commercially available spherical fused silica includes “SO-C2”, “SO-C1”, “YC100C”, and “YA010C” manufactured by Admatechs.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less from the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment and preventing the occurrence of projections when forming a thin film, 1 μm or less is more preferred, 0.7 μm or less is more preferred, and 0.5 μm or less, 0.3 μm or less, or 0.15 μm or less is even more preferred. On the other hand, from the viewpoint of obtaining a resin varnish having an appropriate viscosity when forming the resin varnish and having good handleability, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more. , 0.05 μm or more is more preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, it can be measured by preparing a particle size distribution of the inorganic filler on a volume basis by using a laser diffraction type particle size distribution measuring device, and setting a median diameter as an average particle size. As the measurement sample, a sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, "LA-500", "LA-750", "LA-950", etc. manufactured by Horiba, Ltd. can be used.

  From the viewpoint of increasing the moisture resistance and dispersibility of the inorganic filler, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based coupling agents And the like, and is preferably treated with one or more surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM803” (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane), and the like.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferred. On the other hand, from the viewpoint of preventing an increase in the melt viscosity at the melt viscosity or sheet form a resin varnish, preferably 1 mg / ^{m 2} or less, more preferably 0.8 mg / ^{m 2} or less, 0.5 mg / ^{m 2} or less is more preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the inorganic filler after the surface treatment is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. or the like can be used.

-(B) Epoxy resin-
As the epoxy resin, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, trisphenol epoxy resin, naphthol novolak epoxy resin, Phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, containing spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. One epoxy resin may be used alone, or two or more epoxy resins may be used in combination.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C. (hereinafter, referred to as “liquid epoxy resin”), and having three or more epoxy groups in one molecule, It is preferable to include a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, a resin composition having excellent flexibility can be obtained. Further, the breaking strength of the cured product of the resin composition is also improved.

  Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, phenol novolak epoxy resin, and alicyclic epoxy resin having an ester skeleton. And an epoxy resin having a butadiene structure, and more preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, and a naphthalene epoxy resin. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, and “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US” and “jER828EL” manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. “ZX1059” (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” manufactured by Daicel Corporation ] (Ester skeleton Alicyclic epoxy resin) having, "PB-3600" (epoxy resin having a butadiene structure) and the like. These may be used alone or in combination of two or more.

  Examples of the solid epoxy resin include a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferred. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene-type tetrafunctional epoxy resin), “N-690” (cresol novolac-type epoxy resin), and “HP-4700” manufactured by DIC Corporation. N-695 "(cresol novolac epoxy resin)," HP-7200 "(dicyclopentadiene epoxy resin)," HP-7200HH "," EXA7311 "," EXA7311-G3 "," EXA7311-G4 "," EXA7311 " -G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN-502H "(Trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.," NC7000L "(naphthol novolak type epoxy resin)," NC3000H " "," NC3000 "," NC3000L "," N 3100 "(biphenyl type epoxy resin)," ESN475V "(naphthol type epoxy resin)," ESN485 "(naphthol novolak type epoxy resin)," YX4000H "," Mitsubishi Chemical Corporation " “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd. "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. No.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the ratio by weight (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, i) when used in the form of a resin sheet, moderate tackiness is obtained. Ii) When used in the form of a resin sheet. And iii) an effect of obtaining a cured product having a sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 4 is still more preferable.

  The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That is all. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exerted, but is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

  In the present invention, the content of each component in the resin composition is a value when the nonvolatile component in the resin composition is 100% by mass, unless otherwise specified.

  The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, further preferably from 80 to 2,000, and still more preferably from 110 to 1,000. When the content falls within this range, the crosslinked density of the cured product becomes sufficient and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing one equivalent of an epoxy group.

  The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and still more preferably from 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-(C) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and includes, for example, an active ester-based curing agent, a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, a benzoxazine-based curing agent, and a carbodiimide. Curing agents, active ester curing agents, and the like. One type of curing agent may be used alone, or two or more types may be used in combination.

  As the phenol-based curing agent and the naphthol-based curing agent, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferred from the viewpoint of obtaining an insulating layer having excellent adhesion strength to the conductor layer, and a triazine skeleton-containing phenol-based curing agent. Alternatively, a naphthol-based curing agent containing a triazine skeleton is more preferable. Among them, a phenol novolak resin containing a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength to a conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., and “MEH-7851” manufactured by Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD-2090" manufactured by DIC Corporation. And the like. Specific examples of the triazine skeleton-containing phenol novolak curing agent include, for example, "LA-3018-50P" manufactured by DIC Corporation.

  The cyanate ester-based curing agent is not particularly limited. For example, novolak type (phenol novolak type, alkylphenol novolak type) cyanate ester type curing agent, dicyclopentadiene type cyanate ester type curing agent, bisphenol type (bisphenol A type, (Bisphenol F type, bisphenol S type, etc.) cyanate ester-based curing agents, and prepolymers in which these are partially triazined. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), and 4,4′-ethylidene diphenyl Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Bifunctional cyanate resins such as 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether and bis (4-cyanatephenyl) ether, phenol novolak and cresol novolak Invite from etc. Polyfunctional cyanate resin is, these cyanate resins prepolymers and the like obtained by partly triazine of. Specific examples of the cyanate ester-based curing agent include “PT30” and “PT60” (both are phenol novolac-type polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Is a tripolymer which is triazine-modified to form a trimer).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., and “Pd” and “Fa” manufactured by Shikoku Chemicals.

  Specific examples of the carbodiimide-based curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Inc.

  As the active ester curing agent, an active ester compound having two or more active ester groups in one molecule is preferable, and examples thereof include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. An active ester compound having two or more ester groups having a high reaction activity in one molecule such as the above is preferably used. The active ester curing agent may be used alone or in combination of two or more.

  From the viewpoint of improving heat resistance, an active ester compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound and a thiol compound is more preferable, and a carboxylic acid compound and an aromatic compound having a phenolic hydroxyl group are preferred. Is more preferably an aromatic compound having two or more active ester groups in one molecule, and a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group. An aromatic compound obtained by reacting an aromatic compound with an aromatic compound, and more preferably an aromatic compound having two or more active ester groups in one molecule. The active ester compound may be linear or branched. Further, if the carboxylic acid compound having at least two or more carboxy groups in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be increased, and if the compound has an aromatic ring, Heat resistance can be increased.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 (preferably 2 to 10, more preferably 2 to 8) carbon atoms and an aromatic carboxylic acid having 7 to 20 (preferably 7 to 10) carbon atoms. Carboxylic acids. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, and itaconic acid. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Above all, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable.

  The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

  Examples of the phenol compound include a phenol compound having 6 to 40 (preferably 6 to 30, more preferably 6 to 23, and still more preferably 6 to 22) carbon atoms. Preferred specific examples thereof include hydroquinone, Resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-type diphenol. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may be used.

  The naphthol compound includes, for example, a naphthol compound having 10 to 40 (preferably 10 to 30, more preferably 10 to 20) carbon atoms, and preferable specific examples thereof include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. As the naphthol compound, naphthol novolak may be used.

  Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, phosphorus-containing oligomers having a phenolic hydroxyl group are preferred, and catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol, phenol novolak, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, , 6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolak, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, and 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol Rac, a phosphorus atom-containing oligomer having a phenolic hydroxyl group is even more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus having a phenolic hydroxyl group Atom-containing oligomers are particularly preferred, and dicyclopentadiene-type diphenols are particularly preferred.

  The thiol compound is not particularly restricted but includes, for example, benzenedithiol, triazinedithiol and the like.

  Preferred specific examples of the active ester curing agent include an active ester compound having a dicyclopentadiene-type diphenol structure, an active ester compound having a naphthalene structure, an active ester compound having an acetylated phenol novolak, and a benzoylated phenol novolak. Active ester compounds containing an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group, including an active ester compound containing a dicyclopentadiene-type diphenol structure, and a naphthalene structure. An active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group is more preferable. In the present invention, the “dicyclopentadiene-type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As the active ester curing agent, an active ester compound disclosed in JP-A-2004-277460 or JP-A-2013-40270 may be used, or a commercially available active ester compound may be used. Commercially available active ester compounds include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000L-65M" (manufactured by DIC Corporation) An active ester compound having a phenolic structure), “9416-70BK” (manufactured by DIC Corporation) (an active ester compound having a naphthalene structure), and “DC808” (manufactured by Mitsubishi Chemical Corporation) (an active ester containing an acetylated phenol novolak) Compound), "YLH1026" (active ester compound containing a benzoylated phenol novolak) manufactured by Mitsubishi Chemical Corporation, and "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

  From the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, the content of the curing agent in the resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. preferable. The upper limit of the content of the curing agent is not particularly limited, but is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

  Further, when the number of epoxy groups of the (b) epoxy resin is 1, from the viewpoint of obtaining an insulating layer having good mechanical strength, the number of reactive groups of the (c) curing agent is preferably from 0.2 to 2, and from 0.3 to 2. 1.5 is more preferred, and 0.35 to 1 is even more preferred. Here, the “number of epoxy groups in the epoxy resin” is a value obtained by dividing the mass of the solid content of each epoxy resin present in the resin composition by the epoxy equivalent and summing the values for all epoxy resins. Further, the `` reactive group '' means a functional group capable of reacting with an epoxy group, and the `` number of reactive groups '' means a solid content mass of each curing agent present in the resin composition in terms of a reactive group equivalent. This is the sum of all the divided values.

-(D) Organic filler-
As the organic filler, any organic filler that can be used in the production of a printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles, with rubber particles being preferred.

  The rubber particles are not particularly limited as long as the resin particles exhibiting rubber elasticity are subjected to a chemical crosslinking treatment, and are fine particles of a resin insoluble and infusible in an organic solvent, for example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Acrylic rubber particles are exemplified. Examples of commercially available rubber particles include “XER-91” manufactured by Nippon Synthetic Rubber Co., Ltd., “Staphyloid AC3355”, “Staphyloid AC3816”, “Staphyloid AC3401N”, and “Staphyloid AC3401N” manufactured by Aika Kogyo. “Staphyloid AC3816N”, “Staphyloid AC3832”, “Staphyloid AC4030”, “Staphyloid AC3364”, “Staphyloid IM101”, “Paraloid EXL2655”, “Paraloid EXL2602” manufactured by Kureha Chemical Industry Co., Ltd., and the like. .

  The average particle size of the organic filler is preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves or the like, and the particle size distribution of the organic filler is measured using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by making a standard and making the median diameter the average particle diameter.

  The content of the organic filler in the resin composition is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

-(E) Thermoplastic resin-
As the thermoplastic resin, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyether Examples include ether ketone resins and polyester resins. The thermoplastic resins may be used alone or in combination of two or more.

  The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the thermoplastic resin in terms of polystyrene is determined by using LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a calibration curve of standard polystyrene by measuring column temperature at 40 ° C. using chloroform or the like as a mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Phenoxy resins having one or more skeletons selected from the group consisting of a skeleton and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of the phenoxy resin include “1256” and “4250” (both phenoloxy resins containing a bisphenol A skeleton), “YX8100” (phenoxy resin containing a bisphenol S skeleton), and “YX6954” (produced by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin), as well as "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX7553BH30", "YL7553", "YL6794" manufactured by Mitsubishi Chemical Corporation. “YL7213”, “YL7290”, “YL7482” and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electric Butyral 4000-2”, “Electric Butyral 5000-A”, “Electric Butyral 6000-C”, and “Electric Butyral 6000-EP” manufactured by Denki Kagaku Kogyo KK. , S-Lek BH series, BX series, KS series (specifically, "KS-1" etc.), BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

  Specific examples of the polyimide resin include “Licacoat SN20” and “Licacoat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include a linear polyimide (polyimide described in JP-A-2006-37083) obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride, and a polysiloxane skeleton. Modified polyimides such as contained polyimides (polyimides described in JP-A-2002-12667 and JP-A-2000-319386) are exemplified.

  Specific examples of the polyamide-imide resin include “Viromax HR11NN” and “Viromax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide resin include modified polyamide-imides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyether sulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include Polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, and more preferably 1% by mass to 15% by mass.

-(F) Curing accelerator-
The curing accelerator is not particularly limited, and examples thereof include an imidazole-based curing accelerator, an amine-based curing accelerator, a phosphorus-based curing accelerator, and a guanidine-based curing accelerator. The curing accelerator may be used alone or in combination of two or more. The curing accelerator is preferably used in a range of 0.05% by mass to 3% by mass, when the total of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass.

-(G) Flame retardant-
Examples of the flame retardant include organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone-based flame retardants, metal hydroxides, and the like. The flame retardants may be used alone or in a combination of two or more. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 9% by mass. As the flame retardant, a commercially available product may be used, for example, “HCA-HQ” manufactured by Sanko Co., Ltd. and the like.

-Other additives-
The resin composition may further contain other components as necessary. Such other components include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds, and resins such as thickeners, defoamers, leveling agents, adhesion promoters, and coloring agents. Additives and the like.

  In the resin sheet of the present invention, the preferable range of the thickness of the resin composition layer is as described in [Method for Producing Resin Sheet].

  The resin sheet of the present invention can be suitably used as a resin sheet for forming a circuit used by being laminated on an insulating resin layer. By using the resin sheet of the present invention in combination with an insulating resin layer when manufacturing a printed wiring board, an insulating layer having a low surface roughness after the roughening treatment can be realized. Among them, the resin sheet of the present invention can be particularly preferably used as a resin sheet for forming a circuit by a plating process (a resin sheet for forming a circuit by a plating process).

[Laminated sheet]
The resin sheet produced by the method of the present invention has excellent adhesiveness, and can easily form a laminated sheet with various films including an insulating resin layer.

  In one embodiment, the laminated sheet of the present invention includes the resin sheet of the present invention and an insulating resin layer joined to the resin composition layer of the resin sheet.

  As the insulating resin layer, a conventionally known insulating resin layer can be used when forming the insulating layer of the printed wiring board. The thickness of the insulating resin layer is preferably 70 μm or less, more preferably 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of reducing the thickness of the insulating layer. Although the lower limit of the thickness of the insulating resin layer is not particularly limited, it can be generally 1 μm or more, 5 μm or more, 10 μm or more, or the like.

  From the viewpoint of obtaining a thin insulating layer having excellent mechanical strength, the insulating resin layer is preferably a prepreg, but a thermosetting resin composition layer containing no sheet-like fiber base material (hereinafter simply referred to as a “thermosetting resin composition”). Layer) may be used. The thermosetting resin composition layer is not particularly limited as long as it exhibits sufficient hardness and insulating properties after curing, but generally contains an epoxy resin and a curing agent. The type and content of the epoxy resin are as described for the (b) epoxy resin in the above [Resin Sheet]. As the curing agent, the curing agent (c) in the above [resin sheet] may be used. At this time, from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer, the amount ratio of the epoxy resin to the curing agent is determined as follows: [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent] ], Preferably 1: 0.2 to 1: 2, more preferably 1: 0.3 to 1: 1.5, and still more preferably 1: 0.4 to 1: 1. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. From the viewpoint of reducing the coefficient of thermal expansion of the obtained insulating layer and preventing the occurrence of cracks and circuit distortion due to the difference in thermal expansion between the insulating layer and the conductor layer, the thermosetting resin composition layer contains an inorganic filler. Preferably, it further includes. As the inorganic filler, the (a) inorganic filler in the above [resin sheet] may be used. The content of the inorganic filler in the thermosetting resin composition layer is, from the viewpoint of lowering the coefficient of thermal expansion of the obtained insulating layer, when the nonvolatile component in the thermosetting resin composition layer is 100% by mass, It is preferably at least 50% by mass, more preferably at least 55% by mass, still more preferably at least 60% by mass, at least 65% by mass, at least 70% by mass, or at least 75% by mass. The upper limit of the content of the inorganic filler is preferably 95% by mass or less, more preferably 90% by mass or less or 85% by mass or less from the viewpoint of the mechanical strength of the obtained insulating layer. Other components that can be contained in the thermosetting resin composition layer include, for example, (d) an organic filler, (e) a thermoplastic resin, (f) a curing accelerator, and (f) described in the above [Resin Sheet]. g) Flame retardants and "other additives".

  In a preferred embodiment, the laminated sheet of the present invention includes the resin sheet of the present invention and a prepreg joined to the resin composition layer of the resin sheet.

  The prepreg is obtained by impregnating a sheet-like fiber base material with a thermosetting resin composition.

  The thermosetting resin composition used for the prepreg is not particularly limited as long as the cured product has sufficient hardness and insulating properties, and a conventionally known thermosetting resin composition used for forming an insulating layer of a printed wiring board. May be used. For example, a resin composition used for forming the above-mentioned thermosetting resin composition layer may be used. Alternatively, the thermosetting resin composition used for the prepreg may be the same as the resin composition used for forming the resin composition layer in the resin sheet of the present invention.

  The sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as a prepreg base material such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the insulating layer, the thickness of the sheet-shaped fiber base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, 25 μm or less, or 20 μm or less. Although the lower limit of the thickness of the sheet-like fiber base material is not particularly limited, it can be usually 5 μm or more, 10 μm or more.

  The prepreg can be manufactured by a known method such as a hot melt method and a solvent method.

  The thickness of the prepreg is preferably 200 μm or less, more preferably 100 μm or less, even more preferably 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, or 30 μm or less. Although the lower limit of the thickness of the prepreg is not particularly limited, it can be generally 10 μm or more, 12 μm or more, or the like. The thickness of the prepreg can be easily changed by adjusting the impregnation amount of the thermosetting resin composition.

  The laminated sheet of the present invention is manufactured by laminating the resin sheet of the present invention and the insulating resin layer such that the resin composition layer of the resin sheet of the present invention and the insulating resin layer (preferably, prepreg) are joined. be able to. For example, the laminated sheet of the present invention can be manufactured by laminating the resin sheet of the present invention on the insulating resin layer such that the resin composition layer of the resin sheet is bonded to the insulating resin layer.

  The lamination of the resin sheet of the present invention and the insulating resin layer has good workability, and a uniform contact state is easily obtained. Therefore, the resin sheet of the present invention is applied to the insulating resin layer by roll pressing or press pressing. Lamination is preferred. The lamination can be performed using a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  In the production of the laminated sheet, the insulating resin layer may be used in the form of an adhesive sheet including a support and an insulating resin layer bonded to the support. As the support, the same support as that described for the resin sheet may be used.

  When the insulating resin layer is used in the form of an adhesive sheet, a protective film conforming to the support is further provided on the surface of the insulating resin layer that is not bonded to the support (that is, the surface opposite to the support). Can be stacked. As the protective film, the same protective film as described in the above-described method for producing a resin sheet may be used. The adhesive sheet can be wound into a roll and stored, and can be used by peeling off the protective film when manufacturing a laminated sheet.

  The laminated sheet of the present invention can be used as a laminated sheet for forming an insulating layer of a printed wiring board (a laminated sheet for an insulating layer of a printed wiring board). By forming an insulating layer of a printed wiring board using the laminated sheet of the present invention, an insulating layer having low surface roughness after the roughening treatment can be realized. Above all, in the manufacture of a printed wiring board by a build-up method, it can be suitably used as a laminated sheet for forming an insulating layer (a laminated sheet for a build-up insulating layer of a printed wiring board), and a plating process is performed thereon. It can be more suitably used as a laminated sheet for forming an insulating layer on which a circuit is formed (a laminated sheet for a build-up insulating layer of a printed wiring board for forming a circuit by a plating process).

[Laminated plate]
The laminated board of the present invention includes an insulating layer formed by heating the resin sheet of the present invention and the insulating resin layer in a state where the resin composition layer and the insulating resin layer are joined.

In one embodiment, the laminated board of the present invention can be manufactured using the resin sheet of the present invention and the insulating resin layer by a method including the following step (I-1) (hereinafter, referred to as “first embodiment”). Also called.)
(I-1) One or more insulating resin layers are arranged between two resin sheets arranged so that the resin composition layers face each other, and heated and pressed at 200 ° C. or more under reduced pressure. Integral molding process

  The resin sheet and the insulating resin layer used in the first embodiment are as described above. In the first embodiment, the insulating resin layer is preferably a prepreg.

  Step (I-1) can be performed, for example, by using a vacuum heat press device in the following procedure.

  First, a laminated structure in which one or more insulating resin layers are arranged between two resin sheets arranged so that resin composition layers face each other is set in a vacuum heat press device.

  The laminated structure is preferably set in a vacuum heat press device via a cushion paper, a metal plate such as a stainless steel plate (SUS plate), a release film or the like. The laminated structure is, for example, laminated in the order of cushion paper / metal plate / release film / laminated structure (for example, resin sheet / insulating resin layer / resin sheet) / release film / SUS plate / cushion paper, and a vacuum hot press apparatus. Is set to

  Here, the symbol “/” means that components shown sandwiching the symbol are arranged so as to be in contact with each other (the same applies to the description of the laminated structure and the like below).

  Next, a vacuum hot press process of heating and pressing the laminated structure under reduced pressure conditions is performed.

  The vacuum heat press treatment can be performed using a conventionally known vacuum heat press device that presses the laminated structure from both sides with a heated metal plate such as a SUS plate. Examples of commercially available vacuum heat press devices include "MNPC-V-750-5-200" manufactured by Meiki Seisakusho Co., Ltd. and "VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.

  The vacuum hot pressing may be performed only once or may be repeatedly performed two or more times.

In the vacuum hot press treatment, the pressing pressure (pressing force) is preferably 5 kgf / cm ^{2 to} 80 kgf / cm ² (0.49 MPa to 7.9 MPa), and more preferably 10 kgf / cm ^{2 to} 60 kgf / cm ² (0. 98 MPa to 5.9 MPa).

In the vacuum hot pressing, the pressure of the atmosphere, that is, the pressure at the time of decompression in the chamber in which the laminated structure to be processed is stored is preferably 3 × 10 ⁻² MPa or less, more preferably 1 × 10 ⁻² MPa or less. It is.

  In the vacuum hot pressing, the heating temperature (T) is 200 ° C. or higher, preferably 210 ° C. or higher, more preferably 220 ° C. or higher. The upper limit of the heating temperature (T) is not particularly limited, but may be usually 240 ° C. or lower.

  From the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, the vacuum heat press treatment is performed by gradually or continuously increasing the temperature and / or gradually or continuously decreasing the temperature. However, it is preferable to carry out. In such a case, it is preferable that the maximum attained temperature satisfies the desired temperature condition.

  The step (I-1) may be performed using two or more insulating resin layers and further disposing an inner layer substrate between the insulating resin layers. The two or more insulating resin layers may be the same or different.

  In the present invention, the "inner layer substrate" mainly means a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a pattern processing on one or both surfaces of the substrate. Refers to a circuit board on which a formed conductor layer (circuit) is formed. Further, when manufacturing a printed wiring board, an inner circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the “inner layer board” in the present invention.

  In the step (I-1), the resin composition layer of the resin sheet and the insulating resin layer are integrated to form an insulating layer.

In another embodiment, the laminated board of the present invention can be manufactured using the laminated sheet of the present invention by a method including the following steps (II-1) and (II-2) (hereinafter referred to as “second Embodiment ").
(II-1) A step of laminating the laminated sheet on the inner layer substrate such that the insulating resin layer is in contact with the inner layer substrate. (II-2) A step of forming an insulating layer by thermosetting the laminated sheet.

  The laminated sheet and the inner substrate used in the second embodiment are as described above.

  In the step (II-1), the laminated sheet of the present invention is laminated on the inner layer substrate such that the insulating resin layer is in contact with the inner layer substrate.

  The lamination of the laminated sheet and the inner layer substrate in the step (II-1) can be performed, for example, by heat-pressing the laminated sheet to the inner layer substrate from the support side. Examples of a member (hereinafter, also referred to as a “thermocompression member”) for thermocompression bonding the laminated sheet to the inner layer substrate include, for example, a heated metal plate (such as a SUS mirror plate) or a metal roll (SUS roll). It is preferable that the thermocompression bonding member is not pressed directly on the laminated sheet, but is pressed via an elastic material such as heat resistant rubber so that the laminated sheet sufficiently follows the surface irregularities of the inner substrate.

Lamination of the laminated sheet and the inner layer substrate may be performed by a vacuum lamination method. In the vacuum laminating method, the heating temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the pressing pressure is preferably 1 kgf / cm ^{2 to} 18 kgf / cm ² (0.098 MPa to 1.77MPa), more preferably in the range of ^{3kgf / cm 2 ~15kgf / cm 2} (0.29MPa~1.47MPa), bonding time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 Range of seconds. The lamination is preferably performed under a reduced pressure condition of a pressure of 26.7 hPa or less.

  In the step (II-1), the laminated sheet may be laminated on one side of the inner layer substrate, or may be laminated on both sides of the inner layer substrate.

  Lamination of the laminated sheet and the inner layer substrate can be performed by a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  After lamination, the laminated sheet may be smoothed under normal pressure (under atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the above-described lamination. The smoothing treatment can be performed with a commercially available laminator. Note that the lamination and the smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

  In the step (II-2), the laminated sheet is thermally cured to form an insulating layer.

  The conditions of the thermosetting are not particularly limited, and conditions usually employed when forming an insulating layer of a printed wiring board may be used.

  For example, the thermosetting conditions of the laminated sheet vary depending on the compositions of the resin composition layer and the insulating resin layer, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 210 ° C, more preferably 170 ° C). C. to 190.degree. C.) and a curing time in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

  Before heat curing the laminated sheet, the laminated sheet may be pre-heated at a temperature lower than the curing temperature. For example, prior to thermosetting the laminated sheet, the laminated sheet is heated at a temperature of 50 ° C or more and less than 120 ° C (preferably 60 ° C or more and 110 ° C or less, more preferably 70 ° C or more and 100 ° C or less) for 5 minutes or more ( Preheating may be performed for preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes.

  In the step (II-2), both the resin composition layer and the insulating resin layer in the laminated sheet are thermoset, and an integrated insulating layer is formed.

  Regardless of the first embodiment or the second embodiment, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a circuit on the surface of the insulating layer. May be further implemented. Therefore, in one embodiment, the laminate of the present invention includes a circuit formed on the surface of the insulating layer.

  The support may be removed before forming a circuit on the surface of the insulating layer regardless of the first embodiment or the second embodiment. Specifically, in the first embodiment, the support is provided between step (I-1) and step (III), between step (III) and step (IV), or between step (IV) and step ( V). In the second embodiment, the support is provided between step (II-1) and step (II-2), between step (II-2) and step (III), and between step (III) and step (IV). ) Or between step (IV) and step (V). When an organic support is used as the support, the organic support can be peeled off. If a metal support is used as the support, the metal support can be etched away.

  The step (III) is a step of making a hole in the insulating layer, whereby a hole such as a via hole or a through hole can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition layer and the insulating resin layer used to form the insulating layer. The size and shape of the hole may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions usually used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling process using a swelling solution, a roughening process using an oxidizing agent, and a neutralizing process using a neutralizing solution can be performed in this order to roughen the insulating layer. The swelling solution is not particularly limited, but includes an alkali solution, a surfactant solution, and the like, and is preferably an alkali solution. As the alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan KK. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. Although it does not specifically limit as an oxidizing agent, For example, alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in aqueous solution of sodium hydroxide is mentioned. The roughening treatment using an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganate solution is preferably from 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan KK. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include “Reduction Solution Securiganto P” manufactured by Atotech Japan KK. The treatment with the neutralizing solution can be performed by immersing the roughened surface with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes.

  Step (V) is a step of forming a circuit (conductor layer) on the surface of the insulating layer.

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductive layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Including metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper Nickel alloy and copper-titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper A nickel alloy, an alloy layer of copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable. Metal layers are more preferred.

  The conductor layer may have a single-layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc, or titanium, or an alloy layer of a nickel-chromium alloy.

  The thickness of the conductive layer depends on the desired design of the printed wiring board, but is usually 3 μm to 50 μm, preferably 5 μm to 30 μm.

  The conductor layer can be formed by a plating process. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. Hereinafter, an example in which a conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern for exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. After a metal layer is formed on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Thereafter, the unnecessary plating seed layer is removed by etching or the like, so that a conductor layer having a desired wiring pattern can be formed.

  The laminate of the present invention can be used for various purposes depending on its manufacturing method and structure (for example, whether or not an inner layer substrate is used in the first embodiment, and whether or not a circuit is used in the first and second embodiments). obtain. For example, it may be used as an inner layer substrate such as an insulating core substrate or an inner layer circuit board used for manufacturing a printed wiring board, or may be used as a printed wiring board.

[Semiconductor device]
A semiconductor device can be manufactured using a printed wiring board made of the laminated board of the present invention or using a printed wiring board manufactured using the laminated board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction point” is a “point where an electric signal is transmitted on the printed wiring board”, and the point may be a surface or an embedded point. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, and no bump There are a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the “mounting method using the bump-less build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following description, “parts” means “parts by mass” unless otherwise specified.

<Preparation of resin varnish 1>
5 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., a 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent about 169), 5 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation) , Epoxy equivalent: about 144), 20 parts of biphenyl type epoxy resin ("NC3000L", Nippon Kayaku Co., Ltd., epoxy equivalent: about 269), 20 parts, and phenoxy resin ("YX7553BH30", manufactured by Mitsubishi Chemical Corporation), solid content 20 parts of 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) (1: 1 solution) was dissolved in 3 parts of MEK while heating. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolak-based curing agent (hydroxy equivalent: 125, “LA-7054” manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass), and a naphthol-based curing agent (“SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a hydroxyl equivalent of 215 and a solid content of 60% by mass), 10 parts of polyvinyl butyral resin (glass transition temperature 105 ° C., “KS-” manufactured by Sekisui Chemical Co., Ltd.) 16 parts of a 1: 1 mixed solution of ethanol and toluene having a solid content of 20% by mass), 1 part of an amine-based curing accelerator (4-dimethylaminopyridine (DMAP), a MEK solution having a solid content of 5% by mass), 1 part of imidazole-based curing accelerator (“P200-H50” manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution having a solid content of 50% by mass), N-F Silica surface-treated with Nyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs Co., Ltd., Admananosilica, "YC100C", average particle size 0.10 [mu] m, ratio After mixing 43 parts of an MEK slurry having a surface area of 50 m ² / g and a solid content of 30% by mass) and uniformly dispersing the mixture using a high-speed mixer, the mixture was degassed under reduced pressure, and a cartridge filter (“SCP-010” manufactured by Loki Techno Co., Ltd.) Filtration efficiency (manufacturer's nominal value): Resin varnish 1 was prepared by filtration with particles of 1 μm or more cut at 99.9% or more.

<Preparation of resin varnish 2>
12 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238); 12 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185); 12 parts of a pentadiene type epoxy resin ("HP-7200HH" manufactured by DIC Corporation, epoxy equivalent: about 280), and a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. Was dissolved in 12 parts of solvent naphtha and 5 parts of MEK while stirring. After cooling to room temperature, there are 20 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, an active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) and a triazine skeleton. 5 parts of a cresol novolak-based curing agent (hydroxy equivalent: 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts of an MEK solution with a solid content of 5% by mass), and an imidazole-based curing accelerator (2-phenyl-4-methylimidazole, 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., an MEK solution with a solid content of 5% by mass) 2 Part, a spherical silica ((Shin-Etsu Chemical Co., Ltd. “KBM573”) surface-treated with N-phenyl-3-aminopropyltrimethoxysilane) ) Admatechs Ltd., "SO-C1", average particle size 0.30 .mu.m, specific surface area ^{10 m} 2 / g) 14 parts were mixed, after uniformly dispersed in a high-speed rotary mixer, vacuum degassing, further cartridge filter ((Co. ) A resin varnish 2 was prepared by filtration with “SHP-030” manufactured by Loki Techno, filtration efficiency (nominal value of the manufacturer: particles of 2 μm or more were cut by 99.9% or more).

<Preparation of resin varnish 3>
12 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238); 12 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185); 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent: about 280), and a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. Was dissolved in 8 parts of solvent naphtha and 2 parts of MEK while stirring. After cooling to room temperature, 20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) containing a triazine skeleton. 5 parts of a cresol novolak-based curing agent (hydroxy equivalent: 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts of an MEK solution having a solid content of 5% by mass), and an imidazole-based curing accelerator (2-phenyl-4-methylimidazole, 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., an MEK solution having a solid content of 5% by mass) 2 Part, silica surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatex Co., Ltd.) Nanosilica, YA010C ", average particle diameter 0.01 [mu] m, a specific surface area of 300 meters ² / g, a mixture of MEK slurry) 3 parts of solid content of 20 wt%, after uniformly dispersed in a high-speed rotary mixer, vacuum degassing, further cartridge The resin varnish 3 was prepared by filtration with a filter (“SCP-010” manufactured by Loki Techno Co., Ltd., filtration efficiency (manufacturer's nominal value): particles of 1 μm or more were cut by 99.9% or more).

<Preparation of resin varnish 4>
12 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238); 12 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185); 12 parts of a pentadiene type epoxy resin ("HP-7200HH" manufactured by DIC Corporation, epoxy equivalent: about 280), and a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. (1: 1 solution of silica), silica ("Admananosilica, YA010C" manufactured by Admatex Co., Ltd.) surface-treated with phenyltrimethoxysilane ("KBM103" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0 ME having a specific surface area of 300 m ² / g and a solid content of 20% by mass. K slurry) together with 120 parts. After cooling to room temperature, 20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) containing a triazine skeleton. 5 parts of a cresol novolak-based curing agent (hydroxy equivalent: 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts of an MEK solution having a solid content of 5% by mass), and an imidazole-based curing accelerator (2-phenyl-4-methylimidazole, 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., an MEK solution having a solid content of 5% by mass) 2 After mixing the components and uniformly dispersing them with a high-speed rotary mixer, defoaming under reduced pressure, and a cartridge filter (“SCP-010” manufactured by Loki Techno Co., Ltd.) , Filtration efficiency (nominal value by the maker): 1 [mu] m or more particles was filtered with a 99.9% reduction), to prepare a resin varnish 4.

<Preparation of resin varnish 5>
12 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238); 12 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185); 12 parts of a pentadiene type epoxy resin ("HP-7200HH" manufactured by DIC Corporation, epoxy equivalent: about 280), and a phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. Was dissolved in 8 parts of solvent naphtha and 4 parts of MEK while stirring. After cooling to room temperature, 20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) containing a triazine skeleton. 5 parts of a cresol novolak-based curing agent (hydroxy equivalent: 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts of an MEK solution having a solid content of 5% by mass), and an imidazole-based curing accelerator (2-phenyl-4-methylimidazole, 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., an MEK solution having a solid content of 5% by mass) 2 Part, spherical silica ((Shin-Etsu Chemical Co., Ltd. "KBM573") surface-treated with N-phenyl-3-aminopropyltrimethoxysilane (( ) Admatechs Ltd., "SO-C1", average particle size 0.30 .mu.m, specific surface area ^{10 m} 2 / g) 1 part were mixed, after uniformly dispersed in a high-speed rotary mixer, vacuum degassing, further cartridge filter ((Co. ) A resin varnish 5 was prepared by filtration with "SHP-030" manufactured by Loki Techno, filtration efficiency (manufacturer's nominal value): particles of 2 µm or more were cut at 99.9% or more.

<Preparation of resin varnish 6>
12 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 238); 12 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: about 185); 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent: about 280), and a phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass. (1: 1 solution), silica ("Adma Nano Silica, YA010C", manufactured by Admatex, surface-treated with phenyltrimethoxysilane ("KBM103" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size) M of 0.01 μm, specific surface area 300 m ² / g, solid content 20% by mass EK slurry) together with 200 parts. After cooling to room temperature, 20 parts of an active ester-based curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, a toluene solution of a nonvolatile component of 65% by mass) containing a triazine skeleton. 5 parts of a cresol novolak-based curing agent (hydroxy equivalent: 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), an amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts of an MEK solution having a solid content of 5% by mass), and an imidazole-based curing accelerator (2-phenyl-4-methylimidazole, 2P4MZ, manufactured by Shikoku Chemical Industry Co., Ltd., an MEK solution having a solid content of 5% by mass) 2 After mixing the components and uniformly dispersing them with a high-speed rotary mixer, defoaming under reduced pressure, and a cartridge filter (“SCP-010” manufactured by Loki Techno Co., Ltd.) , Filtration efficiency (nominal value by the maker): 1 [mu] m or more particles was filtered with a 99.9% reduction), the resin varnish 6 was prepared.

[Examples 1 to 5, Comparative Examples 1 and 2]
<Manufacture of resin film>
As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, width 550 mm) that had been release-treated with an alkyd resin-based release agent (“AL-5” manufactured by Lintec Corporation) was prepared. . Each resin varnish was coated on the release surface of the support with a die coater at a width of 500 mm and the thickness of the resin composition layer after drying was set to 2 or 3 μm as shown in the following table. Drying zone (5m x 6 zones (zone temperature is set to 70 ° C, 80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, respectively) in order) After passing through a drying zone having a total length of 30 m), the resin film was dried, and then passed through a cooling zone of 3 m (40 ° C.) and wound into a roll to produce each resin film.

<Hazuki evaluation>
With respect to each of the obtained roll-shaped resin films, the appearance of the resin composition layer at a length of 20 m was visually observed, and the number of repellents and the following evaluation criteria were evaluated. In addition, the thing with a dent diameter of 1.5 mm or more was calculated as repelling.
-Evaluation criteria-
：: 1 or less repellent ×: 2 or more repellent

<Evaluation of wrinkles and protrusions>
For each of the obtained roll-shaped resin films, the appearance of the resin composition layer at a length of 20 m was visually observed, and the number of wrinkles and projections and the following criteria were evaluated. In addition, the thing with a length of 3 mm or more was calculated as a wrinkle, and the thing with a diameter of 1.5 mm or more was calculated as a protrusion.
-Evaluation criteria-
：: One or less wrinkles or protrusions X: Two or more wrinkles or protrusions

  From the above table, in Examples 1 to 5 satisfying the relational expression (1), the number of repelling is 1 or less, and the number of wrinkles and protrusions is 1 or less. It can be seen that the occurrence of repelling, wrinkles and projections is suppressed.

  On the other hand, in Comparative Example 1 in which the product of S and V (SV) was less than 1.5 and did not satisfy the relational expression (1), 2 to 4 repelled per m of the resin sheet. In Comparative Example 2 in which the SV exceeded 100 and did not satisfy the relational expression (1), 1 to 3 wrinkles or protrusions were generated per 1 m of the resin sheet.

Claims (8)

(A) a step of coating a resin varnish on the support;
(B) a step of drying the applied resin varnish to form a resin composition layer;
A method for producing a resin sheet, comprising:
The coating of the resin varnish and the drying of the resin varnish are carried out on the same line,
The coating speed Y of the resin varnish is 20 m / min or more,
The content of the non-volatile component in the resin varnish is 30% by mass to 70% by mass,
Resin varnish contains inorganic filler,
When the specific surface area (m ² / g) of the inorganic filler is S and the content (parts by mass) of the inorganic filler is V when the nonvolatile component in the resin varnish is 1 part by mass, The product (SV) satisfies the following relational expression (1),
A method for producing a resin sheet, wherein X and Y satisfy the following relational expression (2), where X is the total length (m) of the drying zone in which the step (B) is performed.
100 ≧ SV ≧ 1.5 Equation (1)
(However, 0.9 ≧ V ≧ 0.003)
Y / X ≧ 0.5 Equation (2) (A) a step of coating a resin varnish on the support;
(B) a step of drying the applied resin varnish to form a resin composition layer;
A method for producing a resin sheet, comprising:
The coating of the resin varnish and the drying of the resin varnish are carried out on the same line,
The coating speed Y of the resin varnish is 20 m / min or more,
The content of the non-volatile component in the resin varnish is 30% by mass to 70% by mass,
Resin varnish contains inorganic filler,
Step (B) uses a drying zone of 3 or more and 20 or less,
When the specific surface area (m ² / g) of the inorganic filler is S and the content (parts by mass) of the inorganic filler is V when the nonvolatile component in the resin varnish is 1 part by mass, A method for producing a resin sheet, wherein a product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Equation (1)
(However, 0.9 ≧ V ≧ 0.003) The thickness of the resin composition layer is 5μm or less, The method according to claim 1 or 2. The specific surface area S of the inorganic filler is ^{5 m} 2 / g or more, The method according to any one of claims 1-3. The specific surface area S of the inorganic filler, ^{5 m} 2 / g or more 500m ² / g or less, The method according to any one of claims 1-4. The method according to any one of claims 1 to 5 , wherein the content V of the inorganic filler is 0.5 parts by mass or less. The method according to any one of claims 1 to 6 , wherein the coating speed Y of the resin varnish is 25 m / min or more. The method according to any one of claims 1 to 7 , wherein the resin sheet is a resin sheet used by being laminated on an insulating resin layer.