JP2016155079A - Method for producing resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin sheet which suppresses repelling of a resin varnish and occurrence of wrinkles and projections, and is excellent in productivity, even when a coating speed of the resin varnish increases.SOLUTION: A method for producing a resin sheet includes: a step (A) of applying a resin varnish onto a support body; and a step (B) of subjecting the applied resin varnish to drying treatment to form a resin composition layer. A coating speed Y of the resin varnish is 20 m/minutes or more, and the resin varnish contains an inorganic filler. When a specific surface area (m/g) of the inorganic filler is represented by S, and a content (pts.mass) of the inorganic filler when a nonvolatile component in the resin varnish is 1 pts.mass is represented by V, a product (SV) of S and V satisfies the following relational expression (1): 100≥SV≥1.5 (where 0.9≥V≥0.003).SELECTED DRAWING: None

Description

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

  As a technique for manufacturing a printed wiring board, a build-up method in which circuit-formed conductor layers and insulating layers are alternately stacked is widely used. The insulating layer is generally formed by laminating a resin sheet including 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, etc.).

JP 2014-17301 A

  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. However, in order to improve productivity and cost performance, the resin composition layer production speed (resin varnish application speed) is increased. When raised, the present inventors have found a problem that the resin varnish is easily repelled, and defects such as wrinkles and protrusions occur in the resin composition layer. It has been found that this problem is particularly noticeable when a thin resin composition layer is produced.

  An object of the present invention is to provide a method for producing a resin sheet that is excellent in productivity by suppressing the occurrence of repelling, wrinkles and protrusions of the resin varnish even when the coating speed of the resin varnish is increased.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a resin varnish in which the specific surface area and content of the inorganic filler satisfy a predetermined relationship, and to complete the present invention. It came.

That is, the present invention includes the following contents.
[1] (A) a step of applying a resin varnish on a support;
(B) drying the coated 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,
The resin varnish contains an 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 when the nonvolatile component in the resin varnish is 1 part by mass is V, S and V A method for producing a resin sheet, wherein the product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Formula (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 of [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 Formula (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 resin sheet for circuit formation used by being laminated on an insulating resin layer.

  ADVANTAGE OF THE INVENTION According to this invention, even if it increased the coating speed, it became possible to provide the manufacturing method of the resin sheet which suppressed generation | occurrence | production of the varnish of a resin varnish, wrinkles, and protrusion, and was excellent in productivity.

  Hereinafter, the resin sheet manufacturing method, the resin sheet, the laminated sheet, the laminated plate, and the 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 a region having no resin varnish or a region having an extremely small amount of the resin varnish is formed as a result of the resin varnish repelling on the coated surface of the resin varnish. In the present specification, the repelling of the resin varnish includes both a repelling that occurs immediately after application of the resin varnish and a repelling that occurs in the process of drying the resin varnish. In the present 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.

[Production method of resin sheet]
The method for producing the resin sheet of the present invention comprises:
(A) coating a resin varnish on the support;
(B) drying the coated resin varnish to form a resin composition layer;
Including
The coating speed Y of the resin varnish is 20 m / min or more,
The resin varnish contains an 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 when the nonvolatile component in the resin varnish is 1 part by mass is V, S and V The product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Formula (1)
(However, 0.9 ≧ V ≧ 0.003)

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

  Hereinafter, each process in the manufacturing method of the resin sheet of this invention is demonstrated in detail.

<Process (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, the 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, due to restrictions such as the length of the drying zone for drying the resin varnish, the coating speed of the resin varnish has conventionally been generally less than 20 m / min (in many cases, 10 to 15 m / min). It was. Specifically, since application of the resin varnish and drying of the resin varnish are usually performed on the same line, if the application speed of the resin varnish is increased, the support after application of the resin varnish passes through the drying zone. Speed increases Therefore, in order to sufficiently dry the resin varnish, it is necessary to increase the length of the drying zone. However, the length of the drying zone is limited due to the design of the device, and as a result, the resin varnish is coated. Work speed was limited. A method of quickly drying the resin varnish by setting the temperature of the drying zone to a high level is also conceivable. However, in this method, the solvent in the resin varnish rapidly evaporates, and as a result, the resin varnish is repelled in the process of drying. Tended to occur easily. 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 defects such as wrinkles and protrusions are generated in the resin composition layer. In this respect, in the method for producing a resin sheet of the present invention using the resin varnish in which the specific surface area S and the content V of the inorganic filler satisfy the relational expression (1), the coating speed Y of the resin varnish is 20 m / min or more. Even so, the occurrence of repelling, wrinkles and protrusions of the resin varnish can be suppressed. In the method for producing a resin sheet of the present invention, it is possible to employ a higher coating speed Y while suppressing the repelling of the resin varnish, the generation of wrinkles and protrusions. 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 can usually be 300 m / min or less, 200 m / min or less, 100 m / min or less, etc., from the viewpoint of sufficiently suppressing the repelling of the resin varnish, generation of wrinkles and protrusions.

-Resin varnish-
The resin varnish used in the present invention contains an inorganic filler. When the specific surface area (m ² / g) of the inorganic filler is S and the non-volatile component in the resin varnish is 1 part by mass from the viewpoint of suppressing the occurrence of repellency, wrinkles and protrusions during high-speed coating of the resin varnish When the content (parts by mass) of the inorganic filler is V, the product of S and V (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Formula (1)
(However, 0.9 ≧ V ≧ 0.003)

The product of S and V (SV) 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. Further, from the viewpoint of suppressing generation of wrinkles and protrusions, SV is 100 or less, preferably 95 or less, more preferably 90 or less. In detail, since the wrinkles and protrusions are likely to be generated when the specific surface area S (m ² / g) of the inorganic filler is large, the content V (part by mass) of the inorganic filler may be reduced. If the specific surface area S (m ² / g) is small, repelling is likely to occur, so the content V (parts by mass) of the inorganic filler may be increased. In addition, the specific specific surface area S (m < ² > / g) and content V of an inorganic filler are mentioned 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 the preparation of the resin varnish is not particularly limited as long as the effects of the present invention are not impaired, and a known solvent that can be used for the production of 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, propylene glycol monomethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carb Acetic esters 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, etc. Can be mentioned. A solvent may be used individually by 1 type or may be used in combination of 2 or more type.

  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 from the viewpoint of effectively suppressing the occurrence of repellency, wrinkles and protrusions during high-speed coating of the resin varnish. It is preferable to include a solvent at 120 ° C. or higher. Accordingly, in a preferred embodiment, the solvent includes a solvent having a boiling point of 100 ° C. or higher. From the viewpoint of increasing the Y / X value described later while suppressing the occurrence of repellency, wrinkles and protrusions during high-speed coating of the resin varnish, the solvent has a boiling point of 100 ° C. in addition to a solvent having a boiling point of 100 ° C. or higher. It is suitable 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). Accordingly, 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 less than 100 ° C. is used as the solvent.

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

  The viscosity (23 ° C.) of the resin varnish is 10 mPa · s or more from the viewpoint of suppressing the occurrence of repellency, wrinkles and protrusions and easily controlling the thickness of the resin composition layer even in high-speed coating. Preferably, 30 mPa · s or more is more preferable, and 50 mPa · s or more is more preferable. Although there is no restriction | limiting in particular about the upper limit of the viscosity of a resin varnish, 5000 mPa * s or less is preferable, 4000 mPa * s or less is more preferable, 3000 mPa * s or less is more preferable.

  The viscosity of the resin varnish can be measured using, for example, a rotary (E type) viscometer. Examples of the rotary (E type) viscometer include “RE-80U” manufactured by Toki Sangyo Co., Ltd.

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

-Support-
Examples of the support include a film made of a plastic material, a metal foil, and a 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 polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, 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.). It may be used.

  The support may be subjected to mat treatment or corona treatment on the surface on which the resin varnish is applied. 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 for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

  Although the thickness of a support body is not specifically limited, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  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, the resin varnish can be coated on the support using a coating apparatus such as a die coater, a comma coater, a gravure coater, or a bar coater.

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

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

  The 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 can usually be 150 ° C. or lower, 140 ° C. or lower, and the like.

  Step (B) may be performed using a single drying zone or may be performed using a plurality of drying zones. When using a plurality of drying zones, 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. The upper limit of the number n of drying zones is not particularly limited, but can usually be 20 or less, 15 or less, 10 or less, and the like. When the step (B) is performed 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 through which the substrate passes second is referred to as a “second drying zone”, and the drying zone through which the nth pass is passed. It is also referred to as “nth drying zone” (where 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 the repelling of the resin varnish caused by rapid evaporation of the solvent. The temperature is set to be sufficiently lower than the boiling point of the solvent. When the boiling point (° C.) of the lowest boiling solvent contained in the resin varnish is Tb, the temperature T1 of the first drying zone is generally less than (Tb-10) ° C., (Tb-15) ° C. or less, or ( Tb-20) It is set to below ℃. In this regard, in the present invention using the resin varnish that satisfies the 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 less, more preferably (Tb + 15) ° C. or less, and further preferably (Tb + 10) ° C. or less, from the viewpoint of suppressing the repelling of the resin varnish. It is. Further, from the viewpoint of setting a high Y / X ratio, which will be described later, while suppressing rapid evaporation of the solvent, the temperature T2 of the second drying zone is preferably higher than the temperature T1, and is (T1 + 5) ° C. or higher. More preferably, it is (T1 + 10) ° C. or higher. The upper limit of the temperature T2 of the second drying zone is preferably (T1 + 50) ° C. or less, more preferably (T1 + 40) ° C. or less, further preferably (T1 + 30) ° C. or less, or (T1 + 20) ° C. or less. The temperature Tmax of the drying zone set to the highest temperature is preferably (Tb′−50) ° C. or more, when the boiling point (° C.) of the highest boiling solvent contained in the resin varnish is Tb ′. Preferably, it is (Tb′−40) ° C. or higher. The upper limit of the temperature Tmax is not particularly limited as long as it is within the preferable range of the drying temperature, but is preferably (Tb '+ 10) ° C or less, more preferably (Tb' + 5) ° C or less. In a preferred embodiment, the temperature of the drying zone is set to increase in order from the first drying zone to the nth drying zone.

  A single drying zone that can achieve 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 coating 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 coating speed Y (m / min) described above.

If the total length (m) of the drying zone for carrying out the step (B) is X, X and Y preferably satisfy the following relational expression (2) from the viewpoint of improving the productivity of the resin sheet. The total length of the drying zone refers to the length of the drying zone when a single drying zone is used, and the sum of the lengths of the plurality of drying zones when a plurality of drying zones are used. .
Y / X ≧ 0.5 Formula (2)

  As described above, the coating speed Y of the resin varnish tended to be limited due to the restriction on the total length X of the drying zone. Furthermore, if the coating speed Y of the resin varnish is increased, the resin composition layer is likely to be repelled immediately after coating, and defects such as wrinkles and protrusions may occur in the resin composition layer. Found in In this regard, in the present invention using the resin varnish that satisfies the above relational expression (1), it is possible to achieve a higher Y / X ratio while suppressing the occurrence of the repelling, wrinkles and protrusions 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. Although there is no restriction | limiting in particular about the upper limit of Y / X ratio, Preferably it is 10 or less, More preferably, it is 8 or less, More preferably, it is 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. Further preferred. In addition, when using several drying zones, the length of each drying zone does not have a restriction | limiting in particular, However, 1m-10m are preferable, 2m-8m are more preferable, 3m-7m are further more preferable.

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

  In the present invention, by satisfying the relational expression (1), even when the resin varnish is applied at a high speed to form a thin resin composition layer, the occurrence of repelling, wrinkles and protrusions of the resin varnish is suppressed. can do. For example, even when a thin resin composition layer of 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 is achieved. 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, further preferably 0.4 μm or more, 0.6 μm or more, 0.8 μm or more, Or it is 1 micrometer or more. The thickness of the resin composition layer can be measured using, for example, a contact-type layer thickness meter. Examples of the contact-type layer thickness meter include “MCD-25MJ” manufactured by Mitutoyo Corporation.

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

  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 produced by the method for producing a resin sheet of the present invention, the number of repelling of the resin varnish at a length of 20 m is 1 or less, preferably 0, in visual observation. The repellency indicates that the dent diameter is 1.5 mm or more.

  In the resin sheet produced by the method for producing a resin sheet of the present invention, the number of wrinkles and protrusions of the resin composition layer at a length of 20 m is 1 or less, preferably 0, in visual observation.皺 represents a length of 3 mm or more, and the protrusion represents a diameter of 1.5 mm or more.

  The method for producing a resin sheet of the present invention is a protective film according to the support on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support) after the step (B). The process of providing may be included.

  Although the thickness of a protective film is not specifically limited, For example, it can be set as 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be wound and stored in a roll shape, and can be used by removing the protective film when forming an insulating layer in the production of a printed wiring board.

  The protective film is preferably laminated on the resin composition layer by a roll, press bonding, or the like. Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  The resin sheet produced by the method of the present invention is suitable as a resin sheet for circuit formation used by being laminated on an insulating resin layer. In manufacturing a printed wiring board, an insulating layer having a low surface roughness after the roughening treatment can be realized by using the resin sheet in combination with an insulating resin layer. Especially, it can use especially suitably as a resin sheet (resin sheet for circuit formation by a plating process) for performing circuit formation 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 that satisfies the relational expression (1) and drying it. Hereinafter, the resin composition used for preparation of the resin varnish will be described.

  As a resin composition, the composition containing an inorganic filler, curable resin, and its hardening | curing agent is mentioned, for example. As curable resin, the conventionally well-known curable resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. Accordingly, in one embodiment, the resin composition includes (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, as necessary.

  Hereinafter, the material 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 relational expression (1) is satisfied in relation to the content V of the inorganic filler, but preferably 5 m ² / g or more from the viewpoint of preventing repellency. Preferably they are 7 m < ² > / g or more, 10 m < ² > / g or more, 20 m < ² > / g or more, 30 m < ² > / g or more, and 40 m < ² > / g or more is preferable especially from the point which improves fine wiring formation property. From the viewpoint of preventing wrinkles and protrusions, it is preferably 500 m ² / g or less, more preferably 400 m ² / g or less, and still more preferably 350 m ² / g or less. The specific surface area S of the inorganic filler can be measured by the BET method. Specifically, a molecule having a known adsorption occupation area is 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-occupied 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, and examples of the automatic specific surface area measuring device include “Macsorb HM-1210” manufactured by Mountec Co., Ltd.

  The content of the inorganic filler when the non-volatile component in the resin composition is 1 part by mass, that is, the content V of the inorganic filler when the non-volatile component in the resin varnish is 1 part by mass is 0.003. It is not less than 0.9 parts by mass. Preferably 0.8 parts by mass or less, more preferably 0.6 parts by mass or less, particularly the point of sufficiently improving the plating adhesion even when forming fine wiring and the point of preventing the occurrence of protrusions when forming a thin film 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.

  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, and zirconium tungstate phosphate, and silica is particularly suitable. That. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type. Examples of commercially available spherical fused silica include “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 protrusions when forming a thin film, 1 μm or less is more preferred, 0.7 μm or less is more preferred, 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 and good handleability when forming the resin varnish, 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, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, “LA-500”, “LA-750”, “LA-950”, etc. manufactured by Horiba, Ltd. can be used.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents from the viewpoint of improving moisture resistance and dispersibility. It is preferable that it is processed with 1 or more types of 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), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical “KBM103” (phenyltrimethoxysilane) manufactured by Co., Ltd., “SZ-31” (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned.

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 preferable. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity in the sheet form, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is further included. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler 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 ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount 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. can be used.

-(B) Epoxy resin-
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  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, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, phenol novolac type epoxy resins, and alicyclic epoxy resins having an ester skeleton. And epoxy resins having a butadiene structure are preferred, and bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins and naphthalene type epoxy resins are more preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin)", "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (mixed product 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.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 "(cresol novolac type epoxy resin)," HP-7200 "(dicyclopentadiene type 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) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.,“ ESN485 ”(naphthol novolac type epoxy resin),“ YX4000H ”manufactured by 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) manufactured by Mitsubishi Chemical Corporation, “jER1031S” (tetraphenylethane type epoxy resin), etc. Can be mentioned.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to 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 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 further preferably 20% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That's it. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. 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 an epoxy resin. For example, an active ester curing agent, a phenol curing agent, a naphthol curing agent, a cyanate ester curing agent, a benzoxazine curing agent, and a carbodiimide. System curing agent, active ester curing agent, and the like. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As the phenol-based curing agent and naphthol-based curing agent, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable from the viewpoint of obtaining an insulating layer having excellent adhesion strength with the conductor layer, and a triazine skeleton-containing phenol-based curing agent. Or a triazine skeleton containing naphthol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with the conductor layer. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and 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," "TD2090" manufactured by DIC Corporation Or the like. Specific examples of the triazine skeleton-containing phenol novolak curing agent include “LA-3018-50P” manufactured by DIC Corporation.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening 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 triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 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 novolac and cresol novolac 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 curing agent include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

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

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

  As the active ester curing agent, an active ester compound having two or more active ester groups in one molecule is preferable. For example, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds An active ester compound having two or more ester groups with high reaction activity in one molecule is preferably used. An active ester hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of improving heat resistance, an active ester compound obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is preferable. Among them, an active ester compound obtained by reacting a carboxylic acid compound with at least one 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 Aromatic compounds having two or more active ester groups in one molecule, obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule, and having a phenolic hydroxyl group An aromatic compound obtained by reacting 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. Moreover, if the carboxylic acid compound having at least two or more carboxy groups in a molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring. Heat resistance can be increased.

  Examples of the carboxylic acid compound include an aliphatic carboxylic acid having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and an aromatic having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acid is mentioned. Examples of the aliphatic carboxylic acid include acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like. Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance, 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 phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, 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, dicyclopentadiene type diphenol and the like. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used.

  Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and specific examples include α-naphthol, β-naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  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 novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred, catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol More preferred are phosphorus, phosphorus atom-containing oligomers having phenolic hydroxyl groups, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenols, phosphorus having phenolic hydroxyl groups Atom-containing oligomers are particularly preferred, and dicyclopentadiene type diphenols are particularly preferred.

  The thiol compound is not particularly limited, and examples thereof include benzene dithiol and triazine dithiol.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Active ester compounds containing, active ester compounds obtained by reacting aromatic carboxylic acids and phosphorus atom-containing oligomers having phenolic hydroxyl groups, among which active ester compounds containing dicyclopentadiene-type diphenol structures, naphthalene structures More preferred is an active ester compound containing, an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. 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, active ester compounds disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, and commercially available active ester compounds may also be used. Commercially available active ester compounds include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type diacids) manufactured by DIC Corporation. Active ester compound containing a phenol structure), “9416-70BK” (active ester compound containing a naphthalene structure) manufactured by DIC Corporation, “DC808” (active ester compound containing phenol novolac acetylated product) manufactured by Mitsubishi Chemical Corporation Compound), "YLH1026" (active ester compound containing a benzoylated product of 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 more preferably 10% by mass or more. preferable. Although the upper limit of content of a hardening | curing agent is not specifically limited, 40 mass% or less is preferable, 35 mass% or less is more preferable, and 30 mass% or less is further more preferable.

  Moreover, when (b) the number of epoxy groups of the epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, (c) the number of reactive groups of the curing agent is preferably 0.2 to 2, preferably 0.3 to 1.5 is more preferable, and 0.35 to 1 is more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. Further, “reactive group” means a functional group capable of reacting with an epoxy group, and “reactive group number” means the solid content mass of each curing agent present in the resin composition in terms of 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. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particle is not particularly limited as long as it is a fine particle of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Examples of commercially available rubber particles include “XER-91” manufactured by Nippon Synthetic Rubber Co., Ltd., “Staffyroid AC3355”, “Staffyroid AC3816”, “Stuffyroid AC3401N”, “Aka Kogyo Co., Ltd.”, “ “Staffyroid AC3816N”, “Stuffyroid AC3832”, “Stuffyroid AC4030”, “Stuffyroid AC3364”, “Stuffyroid IM101”, “Paraloid EXL2655”, “Paraloid EXL2602” manufactured by Kureha Chemical Industry Co., Ltd., etc. .

  The average particle diameter of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and the particle size distribution of the organic filler is measured by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a standard and setting the median diameter as 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-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin 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 polystyrene-reduced weight average molecular weight of the thermoplastic resin is 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 standard polystyrene calibration curve by measuring the 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, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX7553BH30", "YL7553", "YL6794" manufactured by Mitsubishi Chemical Corporation, "YL7213", "YL7290", "YL7482", etc. are mentioned.

  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, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. Sleksui 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 “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

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

  Specific examples of the polyethersulfone 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, more preferably 1% by mass to 15% by mass.

-(F) Curing accelerator-
Although it does not specifically limit as a hardening accelerator, For example, an imidazole type hardening accelerator, an amine type hardening accelerator, a phosphorus type hardening accelerator, a guanidine type hardening accelerator etc. are mentioned. A hardening accelerator may be used individually by 1 type, or may be used in combination of 2 or more type. The curing accelerator is preferably used in the 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 an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. Although content of the flame retardant in a resin composition is not specifically limited, Preferably it is 0.5 mass%-10 mass%, More preferably, it is 1 mass%-9 mass%. Commercially available products may be used as the flame retardant, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd.

-Other additives-
The resin composition may further contain other components as necessary. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resins such as thickeners, antifoaming agents, leveling agents, adhesion promoters, and colorants. An additive etc. are mentioned.

  In the resin sheet of the present invention, a preferable range of the thickness of the resin composition layer is as described in “Method for producing resin sheet”.

  The resin sheet of this invention can be used conveniently as a resin sheet for circuit formation used by laminating | stacking on an insulating resin layer. In manufacturing a printed wiring board, an insulating layer having a low surface roughness after the roughening treatment can be realized by using the resin sheet of the present invention in combination with an insulating resin layer. Especially, the resin sheet of this invention can be used especially suitably as a resin sheet (resin sheet for circuit formation by a plating process) for performing circuit formation by a plating process.

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

  In one embodiment, the laminated sheet of the present invention includes the resin sheet of the present invention and an insulating resin layer bonded 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 minimum of the thickness of an insulating resin layer is not specifically limited, Usually, it may be 1 micrometer or more, 5 micrometers or more, 10 micrometers or more, etc.

  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 (hereinafter simply referred to as “thermosetting resin composition” not containing a sheet-like fiber base material). May be used). The thermosetting resin composition layer is not particularly limited as long as it exhibits sufficient hardness and insulation after curing, but generally contains an epoxy resin and a curing agent. The kind and content of the epoxy resin are as described for the (b) epoxy resin in the above [resin sheet]. As the curing agent, the (c) curing agent in the above [resin sheet] may be used. At this time, the amount ratio between the epoxy resin and the curing agent is [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] from the viewpoint of improving the mechanical strength and water resistance of the obtained insulating layer. ], 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 varies depending on the type of the curing agent. From the viewpoint of reducing the coefficient of thermal expansion of the resulting 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. Furthermore, it is preferable to include. 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 reducing the coefficient of thermal expansion of the resulting insulating layer, when the nonvolatile component in the thermosetting resin composition layer is 100% by mass, Preferably it is 50 mass% or more, More preferably, it is 55 mass% or more, More preferably, it is 60 mass% or more, 65 mass% or more, 70 mass% or more, or 75 mass% or more. 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 mechanical strength of the obtained insulating layer. Examples of other components that can be contained in the thermosetting resin composition layer include (d) an organic filler, (e) a thermoplastic resin, (f) a curing accelerator, and ( 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 bonded to the resin composition layer of the resin sheet.

  A prepreg is formed by impregnating a thermosetting resin composition in a sheet-like fiber base material.

  The thermosetting resin composition used for the prepreg is not particularly limited as long as the cured product has sufficient hardness and insulation, and a conventionally known thermosetting resin composition used for forming an insulating layer of a printed wiring board. May be used. For example, you may use the resin composition used for formation of said thermosetting resin composition layer. 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 a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the insulating layer, the thickness of the sheet-like fiber substrate is preferably 50 μm or less, more preferably 40 μm or less, still more preferably 30 μm or less, 25 μm or less, or 20 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, 5 micrometers or more, 10 micrometers or more etc. can be used.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  The thickness of the prepreg is preferably 200 μm or less, more preferably 100 μm or less, still 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 minimum of the thickness of a prepreg is not specifically limited, Usually, it can be 10 micrometers or more, 12 micrometers or more, etc. The thickness of the prepreg can be easily changed by adjusting the amount of impregnation of the thermosetting resin composition.

  The laminated sheet of the present invention is produced by laminating the resin sheet of the present invention and the insulating resin layer so 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 produced by laminating the resin sheet of the present invention on an insulating resin layer such that the resin composition layer of the resin sheet is bonded to the insulating resin layer.

  Since the lamination of the resin sheet and the insulating resin layer of the present invention has good workability and a uniform contact state is easily obtained, the resin sheet of the present invention can be applied to the insulating resin layer by roll crimping or press crimping. Lamination is preferable. 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 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 according to the support is further provided on the surface of the insulating resin layer that is not joined to the support (that is, the surface opposite to the support). Can be stacked. As a protective film, you may use the same thing as the protective film demonstrated with the manufacturing method of the said resin sheet. The adhesive sheet can be wound and stored in a roll shape, and can be used by peeling off the protective film when producing 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 the insulating layer of the printed wiring board using the laminated sheet of the present invention, an insulating layer having a low surface roughness after the roughening treatment can be realized. Above all, in the production of printed wiring boards by the 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 on top of that by a plating process 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 on which a circuit is formed by a plating process).

[Laminated board]
The laminated board of this invention contains the insulating layer formed by heating the resin sheet of this invention, and the insulating resin layer in the state which the resin composition layer and the insulating resin layer joined.

In one embodiment, the laminate of the present invention can be produced by a method including the following step (I-1) using the resin sheet and the insulating resin layer of the present invention (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 pressurized at 200 ° C. or higher under reduced pressure. Integrated molding process

  The resin sheet and 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, using a vacuum hot press apparatus according to the following procedure.

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

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

  Here, the symbol “/” means that the components shown so as to sandwich this are arranged so as to contact each other (the same applies to the description of the laminated structure and the like hereinafter).

  Next, a vacuum hot press process is performed in which the laminated structure is thermocompression bonded under reduced pressure conditions.

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

  The vacuum hot press treatment may be performed only once or may be repeated twice or more.

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

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

  In the vacuum hot press treatment, the heating temperature (T) is 200 ° C. or higher, preferably 210 ° C. or higher, more preferably 220 ° C. or higher. Although the upper limit of heating temperature (T) is not specifically limited, Usually, it can be 240 degrees C or less.

  In the vacuum hot press treatment, from the viewpoint of obtaining an insulating layer having a low surface roughness after the roughening treatment, the temperature is raised stepwise or continuously and / or the temperature is lowered stepwise or continuously. However, it is preferable to implement. In such a case, it is preferable that the highest temperature reaches the desired temperature condition.

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

  In the present invention, the “inner layer substrate” is mainly 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 process on one or both sides of the substrate. A circuit board on which a conductive layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention.

  By 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 laminate of the present invention can be produced by a method including the following steps (II-1) and (II-2) using the laminate sheet of the present invention (hereinafter, “second” Also referred to as “embodiment”).
(II-1) A step of laminating the laminated sheet on the inner layer substrate so that the insulating resin layer is in contact with the inner layer substrate (II-2) A step of thermosetting the laminated sheet to form an insulating layer

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

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

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

The lamination of the laminated sheet and the inner layer substrate may be performed by a vacuum laminating method. In the vacuum laminating method, the heating temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably in the range of 80 ° C. to 140 ° C., and the pressure bonding 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 The range of seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  In 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 | stacking of a lamination sheet and an inner layer board | substrate can be performed with a commercially available vacuum laminator. The commercially available vacuum laminator is as described above.

  After the lamination, the laminated sheets may be smoothed under normal pressure (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 conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

  For example, although the thermosetting conditions of the laminated sheet vary depending on the composition of the resin composition layer and the insulating resin layer, 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. to 190.degree. C.), and the curing time may be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).

  Prior to thermosetting the laminated sheet, the laminated sheet may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the laminated sheet, the laminated sheet is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes or longer ( (Preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  By the step (II-2), both the resin composition layer and the insulating resin layer in the laminated sheet are thermally cured to form an integrated insulating layer.

  Regardless of whether the first embodiment or the second embodiment is different, (III) a step of drilling 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.

  In addition, what is necessary is just to remove a support body before forming a circuit in the surface of an insulating layer irrespective of the difference of 1st Embodiment and 2nd Embodiment. In detail, in 1st Embodiment, a support body is between process (I-1) and process (III), between process (III) and process (IV), or process (IV) and process ( V) may be removed. In 2nd Embodiment, a support body is between process (II-1) and process (II-2), between process (II-2) and process (III), process (III) and process (IV). ) Or between step (IV) and step (V). When an organic support is used as the support, the organic support can be peeled off. When a metal support is used as the support, the metal support can be removed by etching.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like depending on the resin composition layer used for forming the insulating layer, the composition of the insulating resin layer, and the like. The dimensions and shape of the holes 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 for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline 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 Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can carry out by immersing an insulating layer for 1 minute-20 minutes in 30-90 degreeC swelling liquid. Although it does not specifically limit as an oxidizing agent, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment 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 conductor 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. Contains 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- A layer formed from a nickel alloy and a copper / titanium alloy). Above all, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper An alloy layer of nickel alloy or copper / titanium alloy is preferable, and 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, and a single layer of copper is preferable. A metal layer is 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 laminated. 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 nickel / chromium alloy.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, it is 3 micrometers-50 micrometers normally, Preferably it is 5 micrometers-30 micrometers.

  The conductor layer can be formed by a plating process. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the 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 that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  The laminated board of the present invention is used for various applications depending on its production method and structure (for example, whether or not an inner layer substrate is used in the first embodiment, 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 substrate 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 electrical products (for example, computers, mobile phones, digital cameras, and televisions) 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 location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below 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>
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent of about 169), 5 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation) ”, Epoxy equivalent of about 144) 5 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd.“ NC3000L ”, epoxy equivalent of about 269) 20 parts, and phenoxy resin (Mitsubishi Chemical Corporation“ YX7553BH30 ”, solid content 20 parts of 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) (1: 1 solution) was dissolved in 3 parts of MEK with stirring with heating. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054 manufactured by DIC Corporation, MEK solution having a solid content of 60% by mass)”, naphthol curing agent (“SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60% by mass), polyvinyl butyral resin (glass transition temperature 105 ° C., manufactured by Sekisui Chemical Co., Ltd. “KS-” 1 "ethanol and toluene 1: 1 mixed solution with a solid content of 20% by weight) 16 parts, amine-based curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by weight) 1 part, 1 part of imidazole-based curing accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution with a solid content of 50% by mass), N-F Silica surface-treated with nil-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs Co., Ltd., Admananosilica, “YC100C”, average particle size 0.10 μm, ratio) After mixing 43 parts of MEK slurry) having a surface area of 50 m ² / g and a solid content of 30% by mass, and uniformly dispersing with a high-speed rotary mixer, vacuum degassing and further cartridge filter (“SCP-010” manufactured by Loki Techno Co., Ltd.) Filtration efficiency (manufacturer's nominal value): Particles of 1 μm or more were filtered by 99.9% or more) to prepare resin varnish 1.

<Preparation of resin varnish 2>
12 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 12 parts of xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), dicyclo 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent of about 280), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass 1 part solution) was dissolved by heating in 12 parts of solvent naphtha and 5 parts of MEK while stirring. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight non-volatile component in toluene), containing triazine skeleton Cresol novolac-based curing agent (hydroxyl group equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by mass of MEK solution having a solid content of 5% by mass, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. (2-phenyl-4-methylimidazole, 2P4MZ), MEK solution having a solid content of 5% by mass) 2 Part, spherical silica ((KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.)) 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. ) “SHP-030” manufactured by Loki Techno, filtration efficiency (manufacturer nominal value): particles having a size of 2 μm or more were cut by 99.9% or more) to prepare a resin varnish 2.

<Preparation of resin varnish 3>
12 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 12 parts of xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), dicyclo 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent of about 280), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass 1: 1 solution) was dissolved in 8 parts of solvent naphtha and 2 parts of MEK with heating and stirring. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight non-volatile component in toluene), containing triazine skeleton Cresol novolac-based curing agent (hydroxyl group equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by mass of MEK solution having a solid content of 5% by mass, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. (2-phenyl-4-methylimidazole, 2P4MZ), MEK solution having a solid content of 5% by mass) 2 Silica treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) (manufactured by Admatechs, Inc. 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 filtering with a filter (“SCP-010” manufactured by Loki Techno Co., Ltd., filtration efficiency (manufacturer nominal value): particles of 1 μm or more were cut 99.9% or more).

<Preparation of resin varnish 4>
12 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 12 parts of xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), dicyclo 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent of about 280), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass Of silica (surface-treated 1: 1 solution) of phenyl trimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) (“Admananosilica, YA010C” manufactured by Admatechs Co., Ltd., average particle size 0) ME with 0.01 μm, specific surface area of 300 m ² / g, solid content of 20% by mass K slurry) was heated and dissolved together with 120 parts. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight non-volatile component in toluene), containing triazine skeleton Cresol novolac-based curing agent (hydroxyl group equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by mass of MEK solution having a solid content of 5% by mass, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. (2-phenyl-4-methylimidazole, 2P4MZ), MEK solution having a solid content of 5% by mass) 2 The parts were mixed and dispersed uniformly with a high-speed rotary mixer, then degassed under reduced pressure, and further 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 (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 12 parts of xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), dicyclo 12 parts of a pentadiene type epoxy resin (“HP-7200HH” manufactured by DIC Corporation, epoxy equivalent of about 280), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation), cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass 1 part solution) was dissolved in 8 parts of solvent naphtha and 4 parts of MEK with stirring. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight non-volatile component in toluene), containing triazine skeleton Cresol novolac-based curing agent (hydroxyl group equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by mass of MEK solution having a solid content of 5% by mass, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. (2-phenyl-4-methylimidazole, 2P4MZ), MEK solution having a solid content of 5% by mass) 2 Part, spherical silica ((KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.)) 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. ) “SHP-030” manufactured by Loki Techno, filtration efficiency (manufacturer nominal value): particles of 2 μm or more were filtered by 99.9% or more) to prepare a resin varnish 5.

<Preparation of resin varnish 6>
12 parts of bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238), 12 parts of xylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), dicyclo 12 parts of a pentadiene type epoxy resin (DIC Corporation "HP-7200HH", epoxy equivalent of about 280), and phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30 mass% cyclohexanone: methyl ethyl ketone (MEK) Silica (surface-treated 1: 1 solution), phenyl trimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.), silica (manufactured by Admatechs, “Admananosilica, YA010C”, average particle size) 0.01 μm, specific surface area 300 m ² / g, solid content 20% by mass M EK slurry) was dissolved by heating together with 200 parts. After cooling to room temperature, 20 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight non-volatile component in toluene), containing triazine skeleton Cresol novolac-based curing agent (hydroxyl group equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), amine-based curing accelerator (4-dimethylaminopyridine (DMAP) ), 2 parts by mass of MEK solution having a solid content of 5% by mass, imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd. (2-phenyl-4-methylimidazole, 2P4MZ), MEK solution having a solid content of 5% by mass) 2 Parts were mixed and dispersed uniformly with a high-speed rotary mixer, and then degassed under reduced pressure. , 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 1-5, Comparative Examples 1-2]
<Manufacture of resin film>
As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, width 550 mm) subjected to release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec Corporation) was prepared. . On the release surface of the support, each resin varnish is coated with a die coater, the width is 500 mm, and the resin composition layer after drying has a coating thickness described in the following table so that the thickness is 2 or 3 μm. Drying zone (5m x 6 zones (zone temperatures set to 70 ° C, 80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, respectively, in order) Each resin film was manufactured by passing through a 3 m cooling zone (40 ° C.) and winding it into a roll.

<Evaluation of repelling>
The appearance of the resin composition layer at a length of 20 m was visually observed for each of the obtained roll-shaped resin films, and evaluated according to the number of repelling and the following evaluation criteria. In addition, it calculated as a repellency that the dent diameter is 1.5 mm or more.
-Evaluation criteria-
○: One or fewer replies ×: Two or more replies

<Evaluation of wrinkles and protrusions>
The appearance of the resin composition layer at a length of 20 m was visually observed for each of the obtained roll-shaped resin films, and evaluated based on the number of wrinkles and protrusions and the following criteria. In addition, the thing with a length of 3 mm or more was calculated as a ridge, and the one with a diameter of 1.5 mm or more was calculated as a protrusion.
-Evaluation criteria-
○: 1 or less wrinkles or protrusions ×: 2 or more wrinkles or protrusions

  From the said table | surface, since Examples 1-5 which satisfy | fill relational expression (1) have the number of repellings 1 or less and the number of wrinkles and protrusions are also 1 or less, even if it applies a resin varnish at high speed It can be seen that the occurrence of repelling, wrinkles and protrusions is suppressed.

  On the other hand, in Comparative Example 1 in which the product of S and V (SV) is less than 1.5 and does not satisfy the relational expression (1), 2 to 4 repels per 1 m of the resin sheet occurred. Further, in Comparative Example 2 where SV exceeds 100 and does not satisfy the relational expression (1), 1 to 3 wrinkles and protrusions are generated per 1 m of the resin sheet.

Claims (8)

(A) coating a resin varnish on the support;
(B) drying the coated 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,
The resin varnish contains an 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 when the nonvolatile component in the resin varnish is 1 part by mass is V, S and V A method for producing a resin sheet, wherein the product (SV) satisfies the following relational expression (1).
100 ≧ SV ≧ 1.5 Formula (1)
(However, 0.9 ≧ V ≧ 0.003)   The method according to claim 1, wherein the thickness of the resin composition layer is 5 μm or less. The method according to claim 1 or 2, wherein X and Y satisfy the following relational expression (2), where X is a total length (m) of the drying zone for carrying out the step (B).
Y / X ≧ 0.5 Formula (2) The method according to any one of claims 1 to 3, wherein the specific surface area S of the inorganic filler is 5 m ² / g or more. 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 to 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 for circuit formation used by being laminated on an insulating resin layer.